materials recycling and environmental sustainability...

Theme-IV

Materials Recycling and Environmental

Sustainability (MRES)

Organized by

5th International Conference on Energy, Environment and Sustainable Development 2018 (EESD 2018)

Millet Husk Ash as Environmental Friendly Material in Cement

Concrete

Narain Das Bheela*, Fareed Ahmed Memonb, Shanker Lal Meghwarc Abdul Wahab Abroa, Irfan

Ali Shara

aM.E Scholar, Department of Civil Engineering, Mehran UET, Jamshoro 76062, Sindh, Pakistan. bProfessor, Department of Civil Engineering, Mehran UET, Jamshoro 76062, Sindh, Pakistan. cLecturer, Department of Civil Engineering, Mehran UET, Jamshoro 76062, Sindh, Pakistan.

Abstract

In this research work, the millet husk ash (MHA) used as a partial replacement material with the different percentages

i.e. 0%, 5%, 10%, 15% and 20% by the weight of cement. The aim of this study is to check the behavior of MHA in

concrete. Millet husk is available in abundant quantity in local agricultural fields and considered as waste after separation

of grains. On the other hand, cement production emits a lot of toxic gases in the atmosphere which causes environmental

pollution and greenhouse gases. Thus, MHA can be used as a cementitious material in the replacement of cement in

concrete for sustainable development. In this consequence, total 30 numbers of standard concrete cubes were cast with

the mix proportion of M25 for checking the compressive strength at different curing ages of 7 and 28 days. Further, at

each proportion of MHA, three cubes were cast and tested in Universal Testing Machine (UTM). The experimental

results show that there is a considerable increment in compressive strength at 5% of MHA when replaced with cement.

In addition, the flow of fresh concrete decreases with an increasing percentage of MHA. Therefore, MHA used in

concrete improve the fresh and harden properties of concrete.

© 2018 Naraind Das Bheel; Prof. Dr. Fareed Ahmed Memon; Shanker Lal Meghwar; Abdul Wahab Abro; Irfan Ali Shar. Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and

Technology, Jamshoro, Pakistan

Keywords: “Millet Husk Ash, environmental pollution, compressive strength, sustainable development”.

1. Introduction:

Concrete is the most broadly utilized and fundamental structural material used in all over the world for the development

of infrastructure [1]. The necessity and significance of concrete in the construction industry are always growing since

its innovation [2]. Lomborg (2007) stated that the use of concrete is greater than any other artificial material on earth

[3-4]. It is an inexpensive, adaptable and tough material and can be converted into several forms and finishes. Mostly,

Concrete reduces the environmental pollution and henceforth concrete structures are designed for long service life [5].

Concrete is an artificial material prepared with ordinary Portland cement and widely used material on the planet earth.

In spite of this, concrete production is one of the universal despairs, having an effect on the environment. The most

alarming effect is global warming which is due to CO2 release during the manufacture of cement [6, 7]. From the year

2005, the country like China manufactured concrete about six billion cubic meters per year that consume the world's

cement production of about 40%. The rate of concrete is comparatively high due to the exuberant cost of its main

integral, the ordinary Portland cement (OPC) [1]. The consumption of OPC was raised from two million tons in 1880 to

about 1.3 billion tons in 1996 and this growth caused the major environmental problem according to Malhorta (2002)

[8]. However, the production of one-ton cement emits approximately one ton of CO2 in the atmosphere [9, 10] and

Malhotra presented a report that manufacturing of cement contributes to being the third biggest carbon-dioxide (CO2)

instigator [8]. Muga et al. (2005) stated that the production of one tone of cement requires about 1.6 tons of natural

resources [11]. Cement is a primary integral of concrete which is not only an expensive but also its manufacture

generates environmental hazardous [1]. Consequently, the industry of cement is striving for other alternatives to reduce

the use of cement by unwanted materials. Many researchers conducted the experimental work by using partially cement

* Corresponding author. Tel.: +0-000-000-0000 ; fax: +0-000-000-0000 .

E-mail address: [email protected]

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replacement materials in concrete with industrial/agricultural wastes such as rice husk ash, sugar cane bagasse ash, corn

cob ash, fly ash, silica fume, wood ash, groundnut husk ash etc. to increase the strength of reinforced concrete structures

and decrease the requirement of ordinary Portland cement [9, 12]. These fillers with pozzolanic properties impart

nominal benefits along with huge amounts of cement replacement to be accomplished [13-19]. Proper use of these

unwanted materials will lead to the enhancement of air quality, the decrease in solid wastes, and the sustainability of the

cement and concrete industry.

Millet crop is grown widely around the world as grains for fodder and human food. Millet is a significant crop in semi-

arid tropics of Asia and Africa [20]. Donough et al (2000) stated that the developing countries produce about 97% of

millet. FAO (2007) presented the report that out of total production of around 28.38 million tons of millet, 40% is

produced in Africa which was ranked as the second biggest producer of millet in the World [21-22].

Further, after processing and separating the grains of millet, the husk is either dumped onsite as waste stuff or spread in

agriculture field and left for months to compost naturally. This composted husk is enriched with minerals essential for

growth of millet plant and act as organic fertilizer. Thus, millet husk (MH) is used as organic fertilizer by a local farmer

who grows this crop. But, on the other hand, this husk when burnet at certain temperature contains cementitious

properties likes cement. Moreover, the Millet Husk Ash (MHA) is obtained by burning the millet husk by using an

uncontrolled burning method [23]. And this ash can be utilized as binding ingredient in the making of concrete. The

number of experimental researches has been carried out by utilizing MHA as a cement substituent material in concrete.

S.M et al. (2015) carried out the research investigation on the hardened properties of concrete intermingled with 0%-

20% of MHA by the weight of cement in concrete. In this research study, the cubes were prepared and cured at 7, 14,

28 and 35 days. It was indicated that the compressive strength measured was -20% by using 10% of MHA in concrete

at 35 days [24].

Solomon et al. (2017) conducted the experimental investigation on the mechanical properties of concrete intermingled

with 0%-40% of MHA as a cement substituent material in concrete. In this study, the concrete blocks were prepared and

cured at 7, 14, 28 days. The result was noted which depicted that the compressive strength measured was -11% by using

10% of MHA in concrete after 28 days [25].

This experimental work was conducted on the use of Millet Husk Ash as a cement substituent material in concrete. It

elaborated the determination of flow of concrete and cubical compressive strength by using various percentages of MHA

as a substituent in concrete.

2. Materials and Methodology:

This research study was investigated to check the workability of fresh and hardened properties of concrete by using

various percentages of MHA as a cement substituent material. For that, five proportion of MHA such as 0%, 5%, 10%,

15%, and 20% were used by the weight of cement. Total 30 cubes (100x100x100mm) were prepared and cured at 7 and

28 days. These concrete cubes were cast for compressive strength at target strength of 25 N/mm2 and ultimately tested

on the universal testing machine (UTM) under the guidance of British Standard (BS) code. For each proportion, three

concrete specimens were cast at every age of curing. This experimental work was completed in the concrete and

structural laboratory, Department of Civil Engineering, MUET Jamshoro, Sindh, Pakistan. Furthermore, the ratio of mix

design and materials used in the experimental work are summarized in Table 1.

Table 1: Mix Design of Concrete

S.No. Mix Ratio Water-cement

ratio

%ages of

MHA

Cement Fine

Aggregates

Coarse

Aggregates

01 1:1.63:2.75 0.54 0 100 100 100

02 1:1.63:2.75 0.54 5 95 100 100

03 1:1.63:2.75 0.54 10 90 100 100

04 1:1.63:2.75 0.54 15 85 100 100

05 1:1.63:2.75 0.54 20 80 100 100

2.1 Materials

2.1.1 Cement

Ordinary Portland Cement (OPC) was used in research work which is locally available in the market of Jamshoro.

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2.1.2 Aggregates

Bolahari Hill sand was used as fine aggregates that passed from #4 sieves and graded to be of zone 2 and the crushed

aggregates were used as coarse aggregates of 20 mm in size which is collected from Petaro Aggregates Crusher Plant.

2.1.3 Millet Husk Ash (MHA)

MHA was achieved by burning the millet husk under the atmosphere for 24 hours at a certain temperature by using the

uncontrolled burning method. The MHA was collected from the region of Tharparkar. And the ash after burning was

left to cool down which was then made to pass through sieve #30 to exclude the coarser particles. After sieving the ash,

it was used in this research.

Photograph 1: Millet Husk Ash

2.1.4 Water:

Clean and drinkable water used in this experimental work which is available in the structural and concrete laboratory of

civil engineering Department, MUET Jamshoro.

3. Result and Discussion: 3.1 Workability of Fresh Concrete:

Standard slump cone was used to determine the workability of fresh concrete in terms of slump loss. The high flow of

fresh concrete was noted at 0% of MHA and lower value of workability of fresh concrete was recorded at 20% of MHA

as a cement replacement material. The flow of fresh concrete blended with MHA is decreased with the increase in the

amounts of MHA. This reduction in workability may be due to the fineness of MHA particles increased the surface area.

Henceforth, MHA particles absorbed some amount of water which caused fall down the flow of concrete. Finally,

decrease due to a shortage of free existing water in the concrete which can impart workability. Experimental values are

given in the graph as shown in Fig. 1.

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Fig. 1. Slump Test

3.2 Compressive Strength of concrete:

The compressive strength of concrete is conducted on cube specimens by following the standard code of British standard

i.e BS EN 12390-3:2009. At each proportion of MHA, three cubes were cast and tested for compressive strength and

finally average of three is taken as a final result. Experimental test results are shown in Table 1 and Table 2 and Figure

2, Figure 3. The maximum compressive strength was recorded 20.90 N/mm2 and 28.80 N/mm2 at 5% of MHA and

minimum compressive strength was noted 17.10 N/mm2 and 23.88 N/mm2 at 20% of MHA as a cement replacement

material at 7 and 28 days respectively. The compressive strength was enhanced due to high amount of silica present in

MHA and its fineness when mixed with concrete increase the transition zone of concrete. This results in maximum

compressive strength up to 10% of MHA. Beyond the 10% of MHA used in concrete, strength starts decreased because

it will affect heat of hydration of cement.

Table 2. Compressive strength of concrete

S.No Curing days % of MHA Average Compressive Strength

(N/mm2)

01 7 days 0% 19.86

02 7 days 5% 20.90

03 7 days 10% 19.29

04 7 days 15% 18.10

05 7 days 20% 17.10

0

0.5

1

1.5

2

2.5

3

0% 5% 10% 15% 20%

Slu

mp

lo

sses

in

in

ch

Workability of Concrete

Percentages of MHA

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Fig. 2. Compressive strength of concrete @ 7 days

Table 02: Compressive Strength of Concrete

S.No Curing days % of MHA Average Compressive Strength

(N/mm2)

01 28 days 0% 26.84

02 28 days 5% 28.80

03 28 days 10% 26.42

04 28 days 15% 24.60

05 28 days 20% 23.88

Fig. 3. Compressive strength of concrete @ 28 days

0

5

10

15

20

25

0% 5% 10% 15% 20%

Co

mp

ress

ive

Str

engt

h (

N/m

m2)

Compressive Strength of Concrete

Percentage of MHA

0

5

10

15

20

25

30

35

0% 5% 10% 15% 20%

Co

mp

ress

ive

Str

en

gth

(N

/mm

2 )

Compressive Strength of Concrete

Percentage of MHA

157


4. Conclusion:

Based on the experimental results obtained in the laboratory, it is concluded that:

The workability of fresh concrete blended with MHA is reduced with the increase in percentages of MHA

content.

The maximum compressive strength was recorded 20.90 N/mm2 and minimum compressive strength was noted

17.10 N/mm2 at 5% and 20% of MHA respectively at 7 days.

The maximum compressive strength was noted 7.3% at 5% of MHA as a cement replacement material

respectively at 28 days.

The minimum compressive strength was measured -11.03% at 20% of MHA by the weight of cement

respectively at 28 days.

References:

[1] O. A. U. Uche, M. Adamu, and M. A. Bahuddeen, “Influence of Millet Husk Ash ( MHA ) on The Properties of Plain Concrete,” Epistemics

Sci. Eng. Technol., vol. 2, no. 2, pp. 68–73, 2012. [2] I. B. Ologunagba, A. S. Daramola, and A. O. Aliu, “Feasibility of using Rice Husk Ash as Partial Replacement for Concrete,” vol. 30, no.

5, pp. 267–269, 2015.

[3] Uche, O.A.U., “Influence of recycled concrete aggregate (RCA) on compressive strength of plain concrete”, Continental J. Engineering Sciences 3, pp 30 – 37, 2008.

[4] Lomborg, B., “Measuring the real state of the world”, the skeptical environmentalist, pp 138, 2007.

[5] J. R. Ajayi, B. O. Rasheed, and O. F. Mojirade, “Exploratory assessment of strength characteristics of millet husk ash ( MHA ) blended cement laterized concrete,” Adv. Appl. Sci. Res., vol. 4, no. 1, pp. 452–457, 2013.

[6] N. Malay, M. Kumar, and J. Kujur, “Effect of Partial Replacement of Cement By Marble Dust on Compressive Strength,” no. June 2016,

pp. 633–643, 2015. [7] John Kamau and Ash Ahmed, “SUITABILITY OF MAIZE COB ASH AS A PARTIAL CEMENT REPLACEMENT”, Juniper online

journal Material Science, vol. 2 no. 5, pp: 01-03, 2017.

[8] Malhotra, V.M, “Introduction: Sustainable Development and Concrete Technology”. Concrete International, 24(7), pp 1-22, 2002. [9] BROOMFIELD J. P., “Corrosion of Steel in Concrete, Understanding, Investigation, and Repair”, Second ed., E & FN SPON; 2007, An

imprint of Chapman & Hall. [10] SCHIESSL P., “Corrosion of Steel in Concrete”, Report of Technical Committee, 60-CSC RILEM, 1988, Chapman and Hall, New York.

[11] Muga, H; Betz, K; Walker, J; Pranger, C, and A. Vidor. “Development of appropriate and sustainable construction materials”. Sustainable

Futures Institute, Michigan Technological University: Michigan, USA. Pp 1- 17, 2005. [12] HUSSAIN R.R., AND ISHIDA T., “Critical Carbonation Depth for Initiation of Steel Corrosion in Fully Carbonated Concrete and

Development of Electrochemical Carbonation Induced Corrosion Model”, International Journal of Electrochemical Science, V. 4, pp.

1178-1195, 2009. [13] DEMIREL BAHAR, “The effect of the using waste marble dust as fine sand on the mechanical properties of the concrete”, International

Journal of the Physical Sciences, V.5, Issue 9, pp. 1372-1380, 2010.

[14] BINICI HANIFI, KAPLAN HASAN, AND YILMAZ SALIH, “Influence of marble and limestone dust as additives on some mechanical properties of concrete”, Scientific Research and Essay, V. 29, pp. 372-379, 2007.

[15] ALSHAHWANY R.B.A., “Effect of Partial Replacement of Sand with Limestone Filler on Some Properties of Concrete”, Al- Rafidain

Engineering, V. 19, Issue 3, pp. 37-48, 2011. [16] HEBHOUB H., AOUN H., BELACHIA M. AND HOUARI H., “Use of Waste Marble Aggregate in Concrete”, Elsevier Journal of

Construction and Building Materials, V. 25, Issue 3, pp. 1167-1171, 2011.

[17] RAI BABOO, KHAN N.H., KUMAR A., AND TABIN R.S., “Influence of Marble Powder/granules in Concrete Mix”, IJCSE, V. 1, No. 4, pp. 827-834, 2011.

[18] ALI ERGUN (2011), “Effects of the usage of diatomite and waste marble powder as partial replacement of cement on the mechanical

properties of concrete”, Construction and Building Materials, V.25, issue 2, pp. 806-812, 2011. [19] CORINALDESI V., MORICONI G., NAIK T.R., “Characteristics of marble powder for its use in mortar and concrete”, NMET/ACI

International Symposium on sustainable development of cement and concrete, 2005, Toronto, Canada.

[20] Salau, M.A. & Balogun, L.A., Building & Environment, vol. 34, pp 165-173, 1999. [21] McDonough, C.M., Rooney, L.W. and Serna-Saldivar, S.O. (2000), “The Millets. Food Science and Technology”, Handbook of Cereal

Science and Technology. CRC Press. 99 2nd Edition: 177–210.

[22] FAO (2007). Food and Agriculture Organization; World Millet Production: Economic and Social Department, the Statistics Division, United Nation.

[23] Obilana, A. B. (2002). Manyasa, E., Millet. In Pseudo-Cereals and Less Common Cereals: Grain Properties and Utilization Potential (P.S.

Belton and T.R.N. Taylor eds): 177-217 New York.

[24] S. M. Auta, A. J. Shiwua, and T. Y. Tsado, “Compressive strength of concrete with millet husk ash (MHA) as a partial replacement for

cement,” Mag. Civ. Eng., vol. 59, no. 7, pp. 74–79, 2015.

[25] S. I. Anowai and J. E. Afunanya, “International Research Journal of Engineering and Technology ( IRJET ) MILLET HUSK ASH AS PARTIAL REPLACEMENT OF CEMENT IN SANDCRETE BLOCK International Research Journal of Engineering and Technology (

IRJET ),” Int. Res. J. Eng. Technol., vol. 4, no. 7, pp. 2–5, 2017.

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Comparing the Effects of Straw and Rice Husk on the Durability of

Mud Brick

Sasui Sasuia*, Warcharin Jinwuthb

a Department of Interior Design, Faculty of Arts & Design, Indus University, Karachi, Pakistan bDepartment of Architecture,Faculty of Architecture, Naresuan University, Phitsanulok, Thailand

Abstract

Mud is a sustainable construction material, which is used to produce bricks for the construction of adobe houses.

Unfortunately, this material is highly susceptible to water due to its poor durability which leads to the material

deterioration and capillary action. To improve the lacking properties of mud brick, two natural stabilizers named straw

and rice husk are commonly used to stabilize the soil. In this study, the influence of straw and rice husk as a stabilizer

was investigated on the stability of mud brick against water, water absorption, linear shrinkage and volumetric shrinkage

by adding these stabilizers in a soil at the ratio of 2% of the dry weight of soil. Results showed significantly improved

performance for the specimens containing stabilizers. Comparatively, straw showed more positive effects than the rice

husk on the stability as the specimen containing straw showed sever deterioration on day 5, water absorption rate 11.87%

and shrinkage of mud specimens with 4.21% & 17.37% for linear and volumetric shrinkage respectively. Whereas the

specimen containing rice husk showed severe deterioration on day 4 instability test, 13.61% absorption rate, the

shrinkage with 4.66 & 24.84 % in linear shrinkage test & volumetric shrinkage test respectively. Thus, this study

concludes that the straw is a more effective stabilizer than rice husk for the production of mud bricks to construct the

local adobe houses in areas affected by flood.

© 2018SasuiSasui, WatcharinJinwuth, Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: Durability; Mudbrick; Natural stabilizers

1. Introduction

Building adobe houses with mud bricks the method of choice for many low-income communities in developing countries

due to the availability of soil which makes the construction affordable [1,2]. The adobe houses are in quantity in many

developing countries, Pakistan, Peru and India are the example of the countries where adobe house are built

commonly[3, 4].In the report of annual disaster statistical review 2011, several developing countries are listed where

flooding occurs frequently [5]. The adobe houses are at high-risk when flood occurs because its durability against water

is poor. The material starts to disintegrate on the long-term exposure to flood water. Besides that, the capillary action

and swelling can occur when the wall surface soak in the flood water, whereas on the drying of wall, the material shrinks

[6-9].

In order to improve the durability of mud brick against water, the soil which is used to produce the brick is stabilized

either with natural stabilizer or with chemical or binders [8, 11]. Stabilizing the soil with natural stabilizers for

construction is a common practice in many developing countries and an economic method of improving the properties

[12]. Straw and rice husk are the natural stabilizers which are used widely as a stabilizer for earthen construction as they

are available in abundance [8, 13, 14]. The effects of straws on the adobe brick’s properties were 1st recognized by

Romans [15]. While the rice husk is used as a stabilizer in either raw and ash form for several masonry materials

* Corresponding author. Tel.: +92 342-3745880.


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including mud, because rice husk provides the cementation properties as it retains the siliceous substance which form

pozzolans [14,16-18].

The effects of straw and rice husk on the properties of mud brick have been investigated in past researches particularly

on the strength properties, thermal conductivity and shrinkage of mud brick. Several researches concluded the negative

effects of straw on the strength of mud brick [11, 15]. However, the positive effect of straw is also determined in the

past studies in increasing the strength and reducing the shrinkage of mud brick [9,11, 19]. Whereas the effects of rice

husk on the properties of mud brick is also investigated in the past researches, and the results showed the positive effects

of rice husk in improving the strength properties and durability of mud brick [13, 14, 20].

In the former studies, the stabilizers were investigated in different parameters such as temperature, soil texture and

testing methods. Considering this factor, the effectiveness of stabilizers cannot be compared referring the results of past

investigations. Therefore, in this study the experiments were conducted to investigate the effects of straws and rice husk

to compare the effects of these stabilizers on the durability of mud brick.

2. Materials & Methods

2.1. Materials collection

The soil used to prepare specimens for the experiments was excavated from the place located in Phitsanulok province

Thailand. The soil consist of 48% sand and 52% fines (clay + silt) which is suitable to producemud brick [21]. The

straw was collected from rice paddy and chopped to the length of 4cm as recommended by Bourdreau [22] and the

rice husk was collected from the nearby rice mill. The prepared straw stabilizer and rice husk stabilizer is shown in

Fig 1: (a) and (b) respectively.

In the former studies the specimens with the addition of straws up to 3.5% and rice husk up to 2% of the weight of

soil showed the positive effects in increasing the properties of adobe brick [20, 9 & 19]. Thus, for the comparison

purpose, the study added each stabilizer with the same proportion, therefore, 2% of dry weight of soil in the dry soil;

the percentage of dry mixture is presented in Table 1. The water was added gradually in the dry mixture until the

optimum plasticity for mixtures was observed and was kneaded manually for the proper consistency of the mixture.

(a) (b) Fig. 1. Stabilizers used in the study; straw (a) and rice husk (b)

Table 1. The proportion of dry mixture

Group Mixture Dry soil (wt. %) Stabilizers (wt. %)

G-1 Soil 100 0

G-2 soil + straw 98 2

G-3 soil + rice husk 98 2

2.2. Preparation of specimens

The method of casting specimens for each experiment was manual. Each prepared mixture group therefore un-

stabilized specimens (G-1), straw stabilized specimen (G-2) & rice husk stabilized specimen (G-3) were used to cast

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the specimens for investigation. To cast 30 prism specimens, the wooden mold of dimension 200 x 150 x 100 mm³

was used. Out of 30 prism specimens, 15 were cast for stability test (5 from each mixture group) as shown in Fig 2:

(a) and 15 specimens (5 from each mixture group) were cast for water absorption test as shown in Fig 2: (b). These

30 prism specimens after drying were measured to calculate volumetric shrinkage. The specimens were dried and

cured for 28 days under the semi-covered sheds at 29 (+ 5) °C average temperature and 69 (+5) % average relative

humidity. The dimension of specimens from each group at the age of 28 days was measured as presented in Table 2.

Whereas for linear shrinkage test, the wooden mold of 600 x 40 x 40 mm³ was prepared to measure the linear shrinkage

of materials of group G-1, G-2 and G-3.

Table 2. Mean average dimension of cured prism specimens

Mixture group Dimension: L x W x H (mm³) Volume (mm³) CV (%)

G-1 190.4 x 145.65 x 72.25 2003619.6 1.22

G-2 198.6 x 148.8 x 76.3 2254793.2 1.10

G-3 188.1 x 142.55 x 74.28 1990913.9 1.80

(a)

(b)

Fig. 2. Adobe specimen at the age of 28

2.3. Test method of stability test by submersion

Since the mud brick disintegrate on the soaking in the standing water of flood, this test will determine the time at

which the un-stabilized and stabilized mud brick samples will disintegrate. Several researches used this method to

determine the stability of brick specimen [23-25]. To conduct this test, the plastic buckets of five US gallons was

filled with the water up to the height of 180 mm to submerge the specimen completely in water as illustrated in Fig 3:

(a). Each submerged specimen was assessed by three people with visual and touch sense as shown in Fig 3: (b). The

specimens were assessed repeatedly until the severe deterioration was observed. To check the specimens’ suitability

for construction, the first assessment was made after 45 minutes of submersion[23]. Each specimen after assessing

was rated accordingly.

(ND) No deterioration: When no visual and by touch damage was observed.

(LD) Light deterioration: When only a slight dent was observed on the specimen.

(MD) Moderate: When the slight dent on the specimen and the slight change in the color of water was observed.

(SD) Severe deterioration: When the major dent was observed on the specimen and the water becomes muddy

and brown in colour due to decomposition of submerged specimens.

2.4. Water absorption test method

The water absorption test was conducted to determine the capability of specimen in resisting the absorption of water

by reducing the volume of voids in the specimen. The durability of specimen was determined on the percentage of

water absorbed by the specimen, where the water absorption rate for a durable specimen is 15% or less than 15%

[26].This test was conducted by following the method recommended in Australian earth building handbook [21].

According to the prescribed method, the cured prisms from each group were immersed in the water for 24 hours. Each

specimen was immersed in a separate plastic bucket of five US gallons weighed 0.7 kg and filled with the water up to

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the level of 100 mm as shown in Fig 3: (c). All buckets were placed under the semi-covered sheds where the average

temperature was 29 (+ 5) °C and average relative humidity was 69 (+5) %. After 24 hours of submersion, each bucket

was drilled from the bottom to drain off the water with extra care to prevent the loss of decomposed material. As soon

as the water drained completely, the immersed weight of specimen was obtained by deducing weight of bucket. All

the buckets were placed at the same place under the same temperature and humidity for drying the specimens to get

the optimum dry weight of specimens. The percentage of water absorbed by each specimen ‘W’ was calculated by

computing the values in “Eq. (1)”.

𝑊% = (𝑊𝑎 − 𝑊𝑏) ÷ 𝑊𝑏 × 100 (1)

2.5. Linear & Volumetric shrinkage test method

The linear shrinkage test is also called Alock’s test, the shrinkage of all the samples was determined following the

procedure recommended in Australian earth building handbook [21]. As per testing procedure, each prepared mixture

therefore G-1, G-2 & G-3 was filled and compacted properly in five wooden molds shown in Fig3 (d). Each mold is

of the dimension of 600 mm length, 40 mm width and 40 mm height. The filled mold with length (L1) dried under

the sun for six days in recorded temperature 30 (+ 5) °C and humidity 50 (+ 5) %. After drying, the shrunk length of

samples (L2) was measured to calculate the shrinkage percentage with the expressed “Eq (2)”.

The percentage of volumetric shrinkage was obtained by calculating the reduction in the size of 10 specimens of each

group therefore G-1, G-2 and G-3 at the age of 28 days.

𝑆ℎ𝑟𝑖𝑛𝑘𝑎𝑔𝑒 % = (𝐿1 − 𝐿2) ÷ 𝐿1 × 100 (2)

(a) (b) (c)

(d)

Fig. 3. Experimental setup

3. Results & Analyses

3.1. Stability by submersion test results

The mode average results of five specimens of each group presented in Table 3 indicating the suitability of specimens

of all groups therefor G-1, G-2 and G-3 for the construction as it showed no deterioration (ND)after 45 minutes of

submersion. The specimens of G-1 after one hour showed light deterioration (LD) and within 24 hours of submersion

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it deteriorated severely (SD). The specimens of group G-2 were not observed under deterioration on the following

day of submersion. However, on day 2 and day 3the specimens were observed in light deterioration (LD). These

specimens deteriorated moderately (MD) on day 4 and severely on day 5. The specimens G-3 remained (ND)in the

1st hour of submersion, it deteriorated lightly (LD) on day 1 and moderately (MD) on day 2 and day 3, while on day

4, the severe deterioration (SD) was observed.

From the results, it can be seen that with the stabilizers, the life of specimens extended and thus the stability of

specimens increased on its submersion in water. Comparatively, straw showed more positive effects on the stability

of water than rice husk.

Table 3. Mode average stability test results

Assessment time G-1 G-2 G-3

45 minutes ND ND ND

1 hour LD ND ND

1 day SD ND LD

2 days - LD MD

3 days - LD MD

4 days - MD SD

5 days SD -

The form of specimens was examined at the stage of severe deterioration after draining the water from buckets. From

Fig 4: it is clear that the un-stabilized specimens (G-1) lose its form as the specimens completely decomposed. While

the straws stabilized specimens (G-2) and rice husk stabilized specimens (G-3) showing maintained form. This is due

the straw and husk fiber glued the soil particles together and prevented the specimen from complete decomposition.

(G-1) (G-2) (G-3)

Fig. 4. Specimens’ form at the stage of severe deterioration

3.2. Water absorption test results

The water absorption “W” percentage presented in table 4 showing the durability for G-2 and G-3 specimens as it

absorbed water less than 15%. While the specimens of group G-1are not considered as a durable brick as it absorbed

water more than 15%. From the results, it is clear that the specimens containing straw and rice husk reduced the

volume of voids in specimens which results in the less absorption of water. The reduction in the volume of void is

proportional to the increase inhomogeneity of material. The absorption of less water in the specimens incorporated

with straw and rice husk indicating the good cementing property of straw and rice husk stabilizer; due to this the

homogeneity of material increased which made the specimen less porous. Comparatively, strap stabilizer (G-2)

showed the maximum effectiveness than rice husk stabilizer (G-3) in reducing the water absorption.

The investigated specimens’ condition was viewed after 24 hours of submersion. From Fig 5: it can be seen that the

material of G-1 specimens disintegrated as it loses its binding property on 24 hours of immersion in the water. The

G-2 and G-3 on the other hand remained in a molded form on 24 hours of immersion in water. From this observation

it is attributed that the specimens remained integrated due to the stronger bond between stabilizer and soil.

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Table 4. Mean average results of water absorption

Prism W (%) CV (%)

G-1 20.63 2.83

G-2 11.87 1.01

G-3 13.61 2.57

(G-1) (G-2) (G-3)

Fig. 5. The specimens’ form after 24 hours of soaking

Since the specimens containing straws and rice husk remained in an integrated form after 24 hours of submersion, the

volume of specimens was measured to observe the swelling of material. The specimens containing straws increased

in the volume by 10.01% and the specimen containing rice husk increased by 10.58% in the volume. Comparing the

swelling of specimens with the shrinkage of specimens which is presented in Table 8, the specimen swelled less than

it supposed to swell. Thus, it indicates that the straw and rice husk on soaking prevented the material from excessive

swelling.

3.3. Linear & volumetric shrinkage test results

The linear shrinkage test results for sample G-1, G-2 and G-3 are presented in Table 5, results showing the reduction

in shrinkage percentage for the samples containing straw (G-2) and rice husk (G-3). The maximum reduction in

shrinkage is observed on the sample containing straw (G-2). Each sample after drying was observed on its appearance,

as illustrated in the Fig 6: it can be seen that the cracks appeared on the un-stabilized sample therefore (G-1) while

the stabilized sample therefore (G-2) and (G-3) did not exhibit cracks after drying.

Table 5. Mean Linear shrinkage results

Prism Linear shrinkage (%) CV (%)

G-1 6.48 2.30

G-2 4.21 1.93

G-3 4.66 2.49

(G-1) (G-2) (G-3)

Fig. 6. The samples of linear shrinkage test after drying

The volumetric shrinkage of 10 prism specimens from each group therefore, G-1, G-2 & G-3 was calculated in

percentage on the shrunk volume of specimens which is given in Table 2. The percentage of volumetric shrinkage of

each group presented in Table 6. showing the un-stabilized specimen (G-1) obtained the shrinkage percentile which

is comparatively higher than the percentage obtained by specimens containing straw (G-1) and rice husk (G-2).

Among all the specimens, straw stabilized specimens (G-2) obtained less shrinkage percentage. Additionally, no

cracks was observed on all the group of specimens as they were cured in sheds and were covered at its early age with

thin polythene sheets to prevent the specimens from rapid dry as rapid dry may lead to the shrinkage cracks [27].

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Table 6. Mean volumetric shrinkage result Table

Prism Volumetric shrinkage (%) CV (%)

G-1 33.21 1.18

G-2 17.37 1.13

G-3 24.84 1.09

The reduction in the shrinkage of stabilized samples indicating that, with the addition of straw and rice husk the

plasticity of material decreased which prevent the material from excessive contraction on drying. Comparatively straw

showed more positive effects in reducing the shrinkage of material.

4. Discussion

The Study revealed the stabilizers i.e. straw and rice husk improved the durability of mud brick specimen. This

improvement is due to the increased bond between the stabilizer and soil particles. Comparing the stabilizers’

performance, it is determined that on the exposure of water, straws maintained its cohesive property more than the rice

husk ash as the maximum improvement was observed in the stability test, water absorption and shrinkage test. In the

past research, the bagasse fiber compared to the rice husk showed the maximum improvement in the properties of adobe

and the reason assumed for the efficient performance of bagasse was its long fiber [13]. The long fibers could also be

reason behind the maximum positive effects of straw. Straw with the long fibers provided the stronger bond in the soil

matrix and results in the efficient performance of specimens on its exposure to water. Based on the results, the straw is

recommended over rice husk as a stabilizer for the construction of adobe houses.

Additionally, the results obtained in this study showing the coefficient of variation (CV) as high as 2.83 %, which is

thus acceptable as the specimens were molded manually [2].

5. Conclusion of study

The impact of 2% straw and 2% rice husk on the mud brick durability was investigated by conducting the field tests.

From the results, the conclusions drawn are as follows:

1. The results of the proposed tests showed the positive performance of the specimens stabilized with straws and

rice husk. However, with the addition of straw, the maximum durability of specimens was observed as it

improved the maximum stability of specimens in the static water, reduced the water absorption and shrinkage

more than the rice husk.

2. The straw and rice husk on the soaking for 24 hours prevented the specimens from excessive swelling. Whereas,

the un-stabilized specimens on soaking disintegrated within 24 hours.

3. Based on the results, the straws are determined as an effective stabilizer and thus the study provides the

guideline that the mud brick if stabilized with straw can improve the performance of adobe structure during

flood event. The improved stability of straw stabilized specimens in static water assures that the straw can

increase the life of mud brick wall by delaying the deterioration of brick in the stagnant flood water. Whereas

the reduction in water absorption for straw stabilized specimen assuring the reduction in capillary action, which

can prevent the wall from cracking and also can prevent the plaster from peeling off. While the reduction in

swelling and shrinkage is ensuring the straw can prevent the wall from excessive change in dimensions on its

soaking in flood water and drying.

Therefore, the stabilizer straw is determined as an appropriate stabilizer for the construction low-cost adobe houses in

the areas affected by flood. Further study should be conducted to compare the effects of straw with other natural

stabilizers. This will provide the guide to building the durable adobe houses with the appropriate natural stabilizer.

Acknowledgment

This paper is a part of M.Arch thesis, we thank the faculty of architecture Naresuan University for providing the

facilities, materials and equipment to conduct this research.

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(1)(2010)1-21.

[2] W.Jinwuth, ‘A study into the earthquake resistance of circular adobe buildings’,Ph.D. thesis,University Technology of Sydney, (2012).

[3] M.Blondet, G.V.Garcia, S.Brzev, A. Rubiños,‘Earthquake-resistant construction of adobe buildings: A tutorial’,EERI/IAEE world housing

encyclopedia, (2003).

[4] PCO, ‘Population and Housing Census 1998’,Government of Pakistan: Statistics Division, (2001).

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[6] O.Ruskulis, ‘Mud as a mortar’, United Kingdom, (2009).

[7] H.Varum, N.Tarque, D.Silveira et.al,‘Structural Behaviour and Retrofitting of Adobe Masonry Buildings’,Structural Rehabilitation of Old

Buildings, Verlag Berlin Heidelberg, 2014,doi: 0.1007/978-3-642-39686-1_2.

[8] B.Sidibe, ‘Understanding Adobe’, Volunteers in Technical Assistance, (1985).

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617-21.

[10] H.Varum, N.Tarque, D.Silveira et.al,‘Structural Behaviour and Retrofitting of Adobe Masonry Buildings’,Structural Rehabilitation of Old

Buildings, Verlag Berlin Heidelberg, 2014, doi: 0.1007/978-3-642-39686-1_2.

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Materials, 22, (2008), 222-7.

[12] H.Houben, H.Guillaud, ‘Earth construction A comprehensive Guide’, First Edition International Technology Development Group, (1994).

[13] P. Lertwattanaruk and J. Choksiriwanna, ‘The physical and thermal properties of adobe brick containing bagasse for earth construction’, Built,

1,(2011), 54-61.

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Architectural/Planning Research and Studies, 5, 187-199, (2007).

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bricks’,Journal of Cultural Heritage, 11,(2010), 309-314.

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Building Materials, 14,(2000), 419-423.

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Wastes in Concrete, (1999)

[18] H.Isah, ‘The effect of rice husk on the chemical properties of clay soil’,Proceeding of 2nd International Conference on Chemical, Biological,

and Environmental Sciences, (2015).

[19] G.Chaudhary, V. Kumar, M. Kumar,‘An experimental study on the capacity assessment of mud brick with impregnated straw’,Indian Institute

of Technology Gandhinagar, (2016).

[20] J.Akinyele, O. Olateju, O. Oikelome,‘Rice husk as filler in the production of bricks using gboko clay’, Nigerian Journal of Technology, 34,

(2015), 672-678.

[21] W. Peter‘The Australian earth building handbook’, Standard Australia International, (2002).

[22] E.H. Boudreau, ‘Making the adobe brick’, Berkeley CA. (1971).

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fiber waste’, International Journal of Engineering Research and application, 6, (2016) 50-59.

[26] H. Molla ‘Study of stabilized mud brick as an alternative building material & development of models’,Thesis, Addis Ababa University,(2012).

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Catalunya, (2013).

166


Antibiotic Assisted Formation of Silver Nanoparticles & it’s Application in Sensors

Mehwish S. Abbasia*, Sirajuddinb, Amber R. Solangia,b a*National Centre of Excellence in Analytical Chemistry,

University of Sindh, Jamshoro

Abstract

Since many years Silver Nanoparticles (AgNPs) have been widely used and introduced as antibacterial material and for

the purification of every kind of environmental liquid/water bodies. These nanoparticles have gained wide attention

because these particles have tremendous applications such as cleaning agents, disinfectants, water treatment, textiles

and applied for drug delivery as medicinally, these AgNPs are also used to reduce burn treatment infections and to

prevent bacterial infections and colonization in human being’s skin and body. In this research Antibiotic (Ofloxacin)

assisted silver nanoparticles have been synthesized by chemical reeducation method, which is a well-known, economical,

low time taking and environmentally friendly method. In this method our drug (Ofloxacin) was used as reducing agent

as well as capping agent. UV-Visible Spectroscopy showed the first indication of formation of Ofloxacin assisted AgNPs,

UV-Visible Spectroscopy excited the typical surface plasmon absorption maxima under certain optimization conditions

at 390 nm. Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) showed the morphology characteristics

of synthesized nanoparticles, it was clearly observed about particles with sponge-like structures, crystalline in nature

and synthesized AgNPs were found to be in the size range of 2 to 27 nm. Ofloxacin assisted AgNPs exhibited highly

sensitive and selective calorimetric sensing of copper metal in linear range of 3.3 µM to 300 µM based on decrease in

intensity with R2 value of 0.976 by UV-Vis spectrophotometry and Limit of detection and Limit of quantification was

found to be 0.44 µM & 1.47 µM. The color variation of AgNPs was changed from yellow to white after addition of

different concentration of copper metal ions. The sensor was highly selective to detect Cu metal in the presence of

various possibly interference ions. The sensor was successfully applied to detect Cu2+ in several types of real water

samples. This finding could be suitable for low-level selective determination of Cu2+ in other types of samples such as

body fluids, vegetable and fruits and so on.

© 2018 “MehwishS.Abbasi Dr. Sirajuddinb,Amber R. Solangia” Selection and/or peer-review under responsibility of Energy and Environmental

Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: “Silver Nanoparticles; Copper; Ofloxacin; Antibiotic; Sensor”

1. Introduction

Nanotechnology is defined as the science of matter manipulation with at least single dimension size from 1 nm to 100 nm [1],

nanotechnology in terms of range and size is a broad field including diverse and many fields of science like, organic chemistry,

microbiology, molecular engineering, physics, energy storage, microfabrication and others [2]. Nanotechnology has variety of

applications in all fields of science and technology from synthesis of Nanosized materials and particles with nanoscale dimensions

and having the control on the atomic scale of matter [3, 4]. The science of Nanotechnology itself is an interesting branch of science

which discus with nanosized materials having at least one dimension in nanoscale range. [5] One of the important aspects of

nanotechnology is the development of more reliable, nontoxic and cheap process for the synthesis of nanoparticles with good chemical

composition. [6]

Nanoparticles are defined as the particles having two or more dimensions in the range between 1 nm to 100 nm. [7] The new field of

* Corresponding author. Tel.: +0-000-000-0000 ; fax: +0-000-000-0000 .


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nanoscience and nanotechnology has revolutionized the globe via its numerous wonderful miraculous properties with unbelievable

applications [8, 9] . One of several properties of nanomaterials is their catalytic aspect owing to decreased size and bigger surface

area [10] . The catalytic properties of nanoparticles are crucial for developing diagnostic tools or sensors to get and check and balance

protocol for getting several useful data for various purposes [11].

Due to unique and diverse chemical, electrical and physical properties, nanomaterials while particularly nanoparticles have attracted

wide attention in the research filed, such unique properties are not apparent in other bulk materials that could be attributed at the large

and small-sized specific surface area [12]. In nanotechnology the results of nanoscience are realized as a science of providing the

Nano range materials with functional facilities. Now, Nanochemistry has become the major growing field of nanoscience. [13] Recent

advances, researches and techniques in the field of nanotechnology have developed and robust the highly selective and sensitive

methods for detection, that help to focus on the conventional technology’s loopholes [14].

Silver nanoparticles is powerful tool in imaging and sensing characterization and application because of amazing optical properties

[14]. Silver have the valuable advantages than gold and other metal nanoparticles because silver nanoparticles are higher coefficient,

sharper bands, high enhancement of the field and higher ratio of scattering to extinction [9, 14]. Silver is known as nontoxic and safe

antibacterial agent, it has been used for many hundred years and it has properties of killing 650 types of diseases causing

microorganisms [11]. Its also observed that silver nanoparticles (AgNPs) have been used as antibacterial material [15]. The

physiochemical applications and properties of silver nanoparticles are necessary for their biodistribution, behavioral changes,

efficiency and safety [16, 17]. Several methods are present to study and synthesize AgNPs such as; hydrothermal, sonochemical [18],

electron beam irradiation, extraction of leave [4], seed extract methods and so on [18]. As compare to all these methods which are

being used since last decade its observed that most economical, environmental friendly and less time taking method is chemical

reduction method in which silver nanoparticles are synthesized by using a drug as capping as well as reducing agent [12, 15].

Silver nanoparticles have been widely used in various sensors and products as their functional components due to extraordinary

optical properties of silver nanoparticles. Because of such properties AgNPs efficiently absorb and scatter the light, the shape and

size of particles depends on the color of synthesized particles, which is a different property than other dyes and pigments [4]. Due to

conduction of electrons the nanoparticles go through strong interaction with light, due to such conduction of electrons on metal surface

area the particles at a specific wavelength undergo collective oscillation due to excitation and such specific wavelength defines many

properties of nanoparticles. [19]

We can also define the optical property of silver nanoparticles in simple way that when the silver nanoparticles are exposed to a

specific wavelength of light the magnetic field of light which is oscillating induces a collective coherent oscillation of the free

electrons, which creates a change separation forming the dipole oscillation along the direction of electric field in respect to the ionic

lattice, the oscillation’s amplitude reaches maximum at a certain frequency this phenomenon is known as surface plasmon resonance

(SPR) [20, 21]. The scattering and absorption properties of silver nanoparticles could be changed by controlling the shape, particle’s

size, refractive index which is adjacent to surface area of particle. It can be also understood from the example that particles having

small size possess refractive index near 400 nm while the particles with large size scatter a lot, have broader peaks and shift towards

longer wavelengths. Beside the optical properties AgNPs can also change their characteristics when particles do aggregation [21].

Ofloxacin is vital antibiotic belongs to a class of drug known as quinolone antibiotic, it is used to treat various infections as (for the

respiratory tract, kidney, soft tissues, skin, it is also used for the treatment of acute pelvic inflammatory disease (PID) caused by

susceptible C. trachomatis or N. gonorrhoeae. [22]. It also stops the growth of bacteria and stops several bacterial infections, in adults

it is used for the treatment of urinary tract infections occurred by gram-negative bacteria. [23]

In this study we have prepared Ofloxacin assisted silver nanoparticles by chemical reduction method. According to our knowledge

this is for the very first time Ofloxacin has been used for the formation of AgNPs and used as optical sensors, this ofloxacin derived

synthesis of AgNPs is also controlled synthesis with monodispersed morphology, its also found that previously no research is done

and no method is available for synthesis of AgNPs with Ofloxacin.

2. Experimental

2.1 Method and Materials used

All chemicals for this study were highly purified and of Analytical grade, all chemicals were used without going through extra

purification. Ofloxacin was purchased from a pharmaceutical company named as (SAMI Pharmaceuticals (Pvt.) Ltd. Karachi),

Sodium Hydroxide (NaOH) and Silver nitrate (AgNO3) from Sigma-Aldrich Chemicals. Metals, Iron (Fe), Potassium (K), Copper

(Cu2+), Chromium (Cr), Leas (Pb), also from Sigma-Aldrich Chemicals. Di ionized water was used for every study of this research.

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2.2 Instrumentation

The characteristics of the composite composition of the synthetic material have been studied using powdered X-ray diffraction (XRD;

Eindhoven, Netherlands with CuKα radiation (λ) = 1.5406 Å) in the range of 5-50°. The morphology and microstructure of the product

have been observed using electron microscopy (SEM; JSM-6701F, JEO, Tokyo, Japan) and atomic microscopy by (SEM; Jeol,

Tokyo, Japan). The UV-Visible measurement was done with its instrument named as (UV-Vis 2600 Shimadzu) in the wavelength

range of 200nm to 800nm. ATR-FT-IR spectrometer. FT-IR spectra between the range 4,000–400 cm-1 were recorded to investigate

the nature of synthesized AgNPs chemical bonds.

2.3 Synthesis of Ofloxacin derived AgNPs

Ofloxacin derived AgNPs synthesis procedure was done by taking 500 µLs of 0.01M standard solution of silver nitrate (AgNO3) in

a test tube of 15 ml and then 5 ml of deionized water was added, after the smooth shaking of silver nitrate and water 400 µLs from

Ofloxacin standard solution of 0.01 M was added in same test tube and at last 10 µLs of 0.1 M solution of Sodium hydroxide (NaOH)

was added to enhance the reaction which created the final volume of 6ml in test tube. The first indication of AgNPs was observed

when the color of solution was turned yellow.

Scheme 1: Illustrate the synthetic procedure of synthesis of Ofloxacin derived AgNPs characterization and applications.

2.4 Sample preparation for XRD, FTIR and SEM analysis

For XRD, SEM and FTIR the solution of yellow color of AgNPs was prepared and taken in 500 ml beaker to heat it on hot plate, the

temperature of plate was maintained 60 °C till the solution was evaporated and became of 10 ml then the 10 ml solution was poured

into petri-dish and again heated on hot plate with temperature 60 °C and within 1 h the black color dry product was obtained which

was washed for two times to remove any unreacted species or impurities, washing was done with deionized water and ethanol, later

the impurities and unreacted antibiotic standard which can disturb characterization were removed. Then the product was carefully

heated in oven at temperature of 60 °C for two hrs. Later, the black silver nanoparticles were scratched from petri dish. The resulted

sample of ofloxacin derived silver nanoparticles were collected in a pin drop for each analysis.

Scheme 2: Illustrates the procedure of synthesis of Ofloxacin derived AgNPs for characterization

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2.5 Procedure for detection of Copper (Cu2+) metal by Ofloxacin derived AgNPs

Synthesized Ofloxacin assisted AgNPs were used to detect the metals, in this case we used different metals such as copper, iron,

nickel, sodium, potassium, mercury, tin, lead and chromium. It was observed that AgNPs changed their color and wavelength by

spiking copper metal while particles remained same by spiking other metals. In this process we added 50 µLs of Cu 0.01 M in 3 mL

of synthesized AgNPs the color changed from yellow to white and wavelength was also changed with change in absorbance which is

further discussed in results.

3. Characterization

For evaluation of functional aspects of synthesized AgNPs characterization is the most important tool. Characterization of

nanoparticles is significant to understand the nature of synthesized nanoparticles, and is done by different analytical techniques, such

as, UV-Visible Spectroscopy, X-Ray diffractometry (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron

Microscopy (SEM. For example UV-Visible Spectroscopy is used to confirm the synthesis of nanoparticles by showing the surface

plasmon resonance at specific wavelength. SEM analysis shows the morphology, shape and size of synthesized nanoparticles. The

determination of crystallinity is performed by X-Ray diffraction.

3.1 UV-Vis Characterization

UV-Visible Spectroscopy was performed to do the optimization and time study of silver nitrate, Ofloxacin and sodium hydroxide to

synthesize AgNPs. The UV-Visible Spectroscopy was done after preparing the solution of synthesize AgNPs in yellow colour, the

instrument showed UV-Visible spectra at 390 nm as shown in Fig 1.

Fig. 1. Ofloxacin derived AgNPs from 1 min to 6 hrs showing no turbidity and no change in colour, the time study of Ofloxacin-AgNPs was

observed for six hours, the wavelength was shifted towards blue shift from 390 to 410 nm. After one week the colour of solution was still the

same yellow which proved the stability of synthesized Ag nanoparticles.

3.2 XRD Analysis

The crystallographic nature of Ofloxacin-AgNPs was characterized by using X-Ray Diffraction (XRD) technique, the chemical

specie’s quantitative resolution and qualitative identification was also determined by XRD technique, this showed that synthesized

AgNPs have Face centered cubic structure (FCC) showing the 4 intense Bragg reflections which can be seen in Fig: 2.

Fig. 2. The recorded XRD powder pattern peaks illustrate intense patterns for the synthesized AgNPs

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The diffracted intensities were recorded from 20° to 80°. Four strong Bragg reflections at 33.45°, 39.35°, 64.75° and 78.05°, this Fig

shows synthesized NPs have two more intense planes and these planes are more prominent which reveals the crystalline nature of

OFX-AgNPs. The crystalline nature of OFX-AgNPs is face cubic centered structure (FCC). Furthermore, the size of these XRD

planes was justified by applying Scherer formula.

In which lambda (λ) reveals wavelength of XRD, the crystalline nanometer size represents by (Dp), K represents the shape factor

having value 0.94 and (β 1/2) represents line broadening at half maximum intensity. OFX-AgNPs average crystallite size was

calculated by above formula was 25 nm and range from 2 nm to 27 nm. XRD study estimated that these OFX-A corresponds to the

planes of (43.22), (27.43), (14.64) and (11.82) respectively which can be indexed face centered cubic (FCC) structure of Ofloxacin

assisted silver nanoparticles.

3.3 SEM Analysis

The structural and morphological properties have been confirmed by using Scanning Electron Microscopy (SEM). The scanning SEM

images were examined under low and high magnification. The captured SEM images of Ofloxacin derived silver nanoparticles show

sponge-like structural features.

Fig. 3. SEM Image of Ofloxacin assisted AgNPs at high resolution of 2 µM shows sponge-like structure and confirms the formation of

nanoparticles which a good image

Fig. 4. SEM Images of Ofloxacin assisted AgNPs at low and high resolutions shows sponge-like structure, the resolution is taken from the

lowest 1 µM to the highest 20 µM.

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3.4 FTIR Analysis

Fourier transform infrared (FT-IR) spectroscopy is an analytical technique used for the characterization and identification of an

organic compound by the transmittance of infrared radiation versus the wave number of the sample. It was used for characterizing

functional groups of reducing as well as capping agent that is involved in the synthesis of nanoparticles. Which have discussed in

Table: 1

Spectrum: 1 FTIR spectrum of Ofloxacin drug and Ofloxacin derived AgNPs (OFX-AgNPs) showing the capping of Ofloxacin, stretching is

described in Table: 1

Table 1: Comparing Spectrum of Ofloxacin and Ofloxacin derived AgNPs

OFLOXACIN Spectrum OFLOXACIN derived AgNPs Spectrum

Primary Amine N-H Stretching at 3370.66 was

observed

Primary Amine N-H Stretching at 3370.66 was not observed due to capping

of drug (Ofloxacin)

Imino Compound N-H stretching at 3293.51 was

observed

Imino Compound N-H stretching 3293.51 was not observed due to capping of

drug (Ofloxacin)

Secondary Amine N-H Stretching at 3173.92 was

observed

Secondary Amine N-H Stretching at 3173.92 was not observed due to capping

of drug (Ofloxacin)

Primary Amine N-H bending at 1630.84 was

observed

Primary Amine N-H bending at 1630.84 was observed was not observed due

to capping of drug (Ofloxacin)

Imino Compound/ Secondary amine N2-H2

bending at 1571.05 was observed

Imino Compound/ Secondary amine N2-H2 bending at 1571.05 was observed

was not observed due to capping of drug (Ofloxacin)

C-H Bending was observed at 14856.18, 1447.60

and 1418.67

C-H Bending was observed at 14856.18, 1447.60 and 1418.67 was not

observed due to capping of drug (Ofloxacin

4. Results and Discussion

4.1 Time Study

Synthesized AgNPs were observed for a week to know their stability and if they become turbid or not, this time study was carried out

with the help of UV-Vis Spectroscopy, firstly min study was done then h and finally days study was observed, it was observed that

synthesized AgNPs were stable for 6 hrs and showed no turbidity for 6 hrs while synthesized AgNPs were kept in test tube in room

temperature for a week.

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Spectrum: UV-Visible Spectrum showing the time study of Ofloxacin derived AgNPs from the time of synthesis to 7 hours, the time study confirms

that our synthesized OFX-AgNPs are stable for 6 hours and could be used for application purpose till 6 hours after synthesis

Table: 2 A comparison of our research work with various reported methods of Colorimetric detection of metal ions

METHOD PRECURSOR

SALT

REDUCING

AGENT

COLORIMETRIC

SENSOR

DETECTED

METAL ION

REFERENCE

Chemical

Reduction

AgNO3 Ofloxacin Ofloxacin-AgNPs Cu2+

Present

Research Work

Green

Synthesis

Ag L-Tyrosine AgNPs Hg2+ [23]

Green

Synthesis

Au L-Tyrosine AuNPs Mn2+ [20]

Chemical

Reduction

Au Glutathione AuNPs Cd2+ [21]

Chemical

Reduction

Ag - AgNPs Cr3+ [19]

Chemical

Reduction

Ag Cysteine AgNPs Hg2+ [18]

Chemical

Reduction

Ag Glutathione AgNPs Co2+ [2]

Chemical

Reduction

Ag Iminodiacetic

acid

AgNPs Pb2+ [5]

Chemical

Reduction

Ag N-Acetyl-L-

cysteine

AgNPs Fe3+ [7]

5. Analytical Approach

5.1 Metal Interferences (Cu2+ detected by AgNPs)

Synthesized Ofloxacin derived AgNPs were used to study the stability, wavelength and absorbance of various metals with synthesized

AgNPs, in this regard 0.01 M solution of different metals such copper, sodium, tin, lead, arsenic, vanadium, cadmium, chromium,

mercury, iron, magnesium, potassium were prepared to know the metal interferences, later different volumes of all metals separately

(one by one) of volume 50 µL were spiked into silver nanoparticles, after observing all metals and results, it was observed that after

5 min colour of silver nanoparticles with copper changed from yellow to white. The change in colour from yellow to white is

considered as visual output and the change in absorption and wavelength was also observed. While no change was observed of AgNPs

with other metals. Hence it was concluded that Ofloxacin derived AgNPs can detect Cu2+ easily.

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Spectrum: UV-Visible Spectrum showing the metal interference with OFX-AgNPs, the peak remains same after spiking the different

metals only change could be observed with spiked Cu2+ in OFX-AgNPs.

5.2 Detection of Copper (Cu2+) in real samples

Here the blank samples of various water samples collected from various localities were first mixed with Ofloxacin derived AgNPs

solution one by one, later 3 ml of Ofloxacin AgNPs were spiked with 50 µLs of 0.01M Copper solution in presence of real water

samples and recorded their wavelengths one by one by UV-Vis spectroscopy.

Table: Analytical figures of merit for the determination of Copper

5.2.1 Real Samples Analysis

The environmental real water samples were taken from different resources, lake water was taken from a lake of Jamshoro,

groundwater was taken from a hand pump present near Al Manzar Jamshoro, tap water was taken from tap of nanotechnology lab.

River water of Indus river Jamshoro was used. All real samples were used as matrix and spiked with synthesized AgNPs to evaluate

recovery of AgNPs and performance of methodology.

Hence for this study all types of water samples (lake, tap, ground and river water) were prepared with Copper (Cu) one by one in

different test tubes of concentration 0.01M, and those prepared solutions were spiked ranging from 1 µL to 50 µLs in synthesized

AgNPs of volume 3ml. This method was repeated 3 times for each reading.

The study was evaluated with UV-Vis Spectroscopy it was observed that tap water with concentration of 0.01M was showing

continues blue shift and absorbance was reduced continuously while the lake water with Cu concentrations of 0.0001M to 0.01M also

showed blue shift and increase in absorbance. The same results were observed for river and groundwater.

174


Spectrum: Optimization of Copper (Cu2+) prepared with deionized water spiked in 3ml of Ofloxacin derived AgNPs.

Graph 1: Calibration curve of AgNPs with spiked Copper of different concentrations showing the linear line calibration with R2 value of

0.9763.

5.2.3 Percentage Recovery of Cu2+ in real samples %Recovery= (Added/Spiked- Recovered/without spiked value)/spiked ×100

Samples Cu added in (µM) Cu recovered in (µM) Recovery (%)

Groundwater 33.33 32.22±0.11 96.66

Lake water 66.7 67.8±0.14 101.6

River water 233.3 232.0±0.13 99.4

Tap water 166.7 164.8±0.16 98.8

175


6. ANALYTICAL ADVANTAGES OF DEVELOPED OFX-AgNPs BASED COLORIMETRIC SENSOR

It is clearly observed that developed colorimetric sensor can detect Cu2+ and Vermox with naked eye; the method to

synthesize this sensor is economical and less time consuming which can help the researchers to perform more work and

applications in environmental pollution and human health. It is also observed that synthesized OFX-AgNPs colorimetric

sensor is stable, low cost, highly sensitive, highly selective and profitable.

7. RECOMMENDATIONS:

It is recommended to public health organizations to concentrate on the exposure of toxic heavy metals

due to their consumption through the use of contaminated water.

Old methods should be replaced by new methods to avoid the toxicity caused due to over usage of

hazardous chemicals, metals and drugs.

An electronic media campaign should be launched for the awareness of public regarding the toxicity

of heavy metals, drugs and other toxic chemicals.

Water should be treated properly before drinking.

The industrial and hospitals waste must be analyzed and purified before consumption and discarding

in rivers and lakes to avoid serious health problems and environmental pollution.

8. Future Direction

The synthesized OFX-AgNPs and its colorimetric sensor in selective and sensitive to Cu2+, in future researchers should

synthesize more nanoparticles like this to remove toxic heavy metals and drugs present in biological and environmental

samples and also use Ofloxacin assisted AgNPs for detection of other metals and drugs.

9. Conclusion

A cost-effective scientific approach for the synthesis of Ofloxacin derived AgNPs was carried out through chemical

reduction method, in which Ofloxacin (an antibiotic) was used as capping and reducing agent and NaOH was used to

enhance the reaction, the yellow transparent colour confirmed the formation of AgNPs which was detected by UV-Vis

spectroscopy with wavelength of 390nm. The pH study showed synthesized AgNPs are neutral in nature with 7 pH.

Then stable sponge-like nanocrystal image of Ofloxacin derived AgNPs was obtained, the sponge-like shape of the

AgNPs was investigate at nanoscale via scanning electron microscopy (SEM). The XRD peaks reveal that the prepared

AgNPs exhibit highly crystalline nature. The synthesized AgNPs were used as optical sensors and they detected copper

in various water samples of environment.

10. Acknowledgment

Support from National Center of excellence in Analytical Chemistry University of Sindh Jamshoro, kind supervision of

Prof. Dr. Sirajuddin and Prof. Dr. Amber Rehana Solangi is acknowledged.

11. REFERENCES [1] Milburn, C., Nanotechnology in the age of posthuman engineering: science fiction as science. Configurations, 2002. 10(2): p. 261-295.

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179-193.

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[12] Junejo, Y. and A. Baykal, Green chemical synthesis of silver nanoparticles and its catalytic activity. Journal of Inorganic and Organometallic

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3303-3321.

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961.

[16] Duan, X. and Y. Li, Physicochemical characteristics of nanoparticles affect circulation, biodistribution, cellular internalization, and

trafficking. Small, 2013. 9(9‐10): p. 1521-1532.

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46(3): p. 622-631.

[18] Lapshin, R., Feature-oriented scanning probe microscopy, in Encyclopedia of nanoscience and nanotechnology2011, American Scientific

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[19] Monteiro-Riviere, N.A., et al., Protein binding modulates the cellular uptake of silver nanoparticles into human cells: implications for in vitro

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[20] Li, W.-R., et al., Antibacterial activity and mechanism of silver nanoparticles on Escherichia coli. Applied microbiology and biotechnology,

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Study Research Group. Archives of Ophthalmology, 1995. 113(10): p. 1257-126

177


Benefits of Building Information Modelling (BIM) on Green

Buildings

Danish Kumara*, Muhammad Saleem Razaa, Shafique Ahmeda and Fida Hussain Siddiquia

aDepartment of Civil Engineering, Mehran University of Engineering and Technology, Jamshoro-76062, Sindh, Pakistan

Abstract

The construction industry is one of the major contributors to climate change/bad environment due to generation of large amount of carbon footprint and using lots of energy in construction projects both before and after completion of project. This research reveals that how Building Information Modelling (BIM) can lower the carbon footprint and energy whose resources are getting expensive day by day. It changes different parameters like design and material, compare schedules and estimates at the early design stage so the construction waste is also reduced. It leads to transformation of an ordinary building into green building that will produce less amount of carbon by reducing the amount of energy and water used in building’s project lifecycle. BIM is an efficient approach because it provides better collaboration of Architect, Engineer, interior designer which help in an efficient Green Building design and construction. The paper also reveals different benefits that BIM may have on green buildings, which can impart its role in green buildings from reduction in waste to lesser energy usage and green energy production.

© 2018 Danish Kumara*, Muhammad Saleem Razaa, Shafique Ahmeda and Fida Hussain Siddiquia

Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group (EEERG), Mehran University

of Engineering and Technology, Jamshoro, Pakistan.

Keywords: Green Buildings; Carbon footprint; Design; Energy; Environment.

1. Introduction

Climate change is the most important issue in the world now a days and AEC (Architecture, Engineering and

Construction) industry are producing lots of waste and tons of carbon which is affecting the environment heavily.

In a new research done by construction blog Bimhow, it is estimated that construction industry produces 50% of

landfill wastes, contributes to 50% of climatic change, 40% of pollution in drinking water and pollutes the air with

an estimate of 23%. In another research by United States Green Building Council (USGBC), the construction

industry uses 40% of world’s energy whose production generate large amount of carbon footprint. It also estimates

that greenhouse gas emissions from commercial buildings will increase by 1.8%. Lots of work is being done to

cater that with techniques like Prefabrication in construction, building more green and passive buildings to reduce

the amount of carbon produced and make this environment better to live for us and future generations. [1-2].

Using BIM for design of green buildings helps in knowing the cost of green building forehand its construction

and reduce the waste too. So, the client is aware of the project outcomes and how it’s going to save the money in

regard of Electricity, fuel and water whose prices are not going to drop down in near future, specifically in

developing countries like Pakistan.

Since past few years the rise of two major trends- construction of green buildings and the use of BIM tools is

witnessed by the AEC industry. Although these trends have progressed independently, and both have made their

distinguished places in building and construction industry, the industry practitioners have realized the remarkable

synergies between the two. The green design can be best served through an integrated design process and BIM is

best known for facilitating the integrated design. Keeping this in view, the usefulness of BIM is widely being

recognized to facilitate the design and construction of green buildings. The use of BIM in green buildings has

great contribution in forecasting, supervising and monitoring the environmental impacts of construction through

its virtual modelling and visualization technology [5]. Therefore, continuous efforts are also being made to explore

a wide range of BIM tools that can be employed for supporting the green construction for example, energy

simulation, lightening and air flow analyses, construction and demolition waste analysis etc. [5]. Some authors

define Green BIM as “to accomplish established sustainability goals by 3D modelling, producing and working

with coordinating building data during project life cycle to enhance the efficiency, quality and performance of the

178


building”. [11]

After witnessing an increasing popularity of the term ‘Green BIM’ in AEC Industry over the last decade, the

growing AEC firms have shifted their focus towards use of BIM in green building practices. Today construction

of Green Buildings using BIM is being promoted by almost every firm and this is just because of its ability to

support sustainable construction through unified design information and collaboration between the architect,

engineer, designer and most importantly the client.[3-5] It should be worth noted that the benefits of BIM on green

buildings is just not limited to the sustainability analysis and the management of design and construction

processes, but it also plays a vital role in the operational, repair, maintenance and demolition processes of the

building (Green building). [3-4-5]. Designs done through BIM are well integrated and more effective sharing of

information is done through BIM which helps engineers and architects to make better designs regarding

sustainability such as day lighting and energy use. [20]. BIM applications perform building analysis and

simulations such as analysis on energy performance. [24, 30, 31, 32, 33]. These applications also analyse carbon

emissions which help in reducing carbon emissions at design stage [28,29]. Through integrated building

performance optimization better green designs can be achieved in early design stage by visualization [24].

Previously the work done is based on benefits or analysis, but this paper does both combines the benefits which

BIM can offer for green buildings and their analysis by using the software like Green Building Studio. The

research shows how Building Information Modelling with use of different software’s reduces the carbon emissions

by reduction in energy use during project lifecycle. Also, it shows how water can be saved during operational

phase by designing through BIM at the start of the project.

2. Literature Review

The purpose of this study is to come up with the benefits of BIM on green buildings by reviewing important

research papers related to green BIM that show us the enhancement of environmental sustainability of buildings

through BIM technology.

Despite the concept of ‘environmental sustainability’ and ‘sustainable development’ being very well known to

the building and construction industry since many past decades, the industry is still considered as immature in

terms controlling and managing the carbon emissions and is criticized as a major carbon emitter [5]. According

to recent facts and figures, the AEC is a major energy consumer, consuming approximately 10% of all global

energy for the manufacturing of building materials. About 30–40% of the total global GHG (greenhouse gas)

emissions take place due to energy consumed during the operation phase of building’s life cycle. [8]. It is also

estimated that construction and demolition waste of the buildings makes up 40% of the total solid waste produced

in the urbanized countries. [5]. After facing the disastrous challenges of global warming, environmental

degradation, the shortage of energy resources and the increasing energy costs, the AEC industry is continuously

being pressurized to minimize their energy consumptions in order to avoid GHG emissions and tackle the

concerns. Therefore, humans in general and AEC industry in particular, have shifted their focus towards the

building and development of low carbon green buildings and Eco cities [6].

The green design can be best served through an integrated design process and BIM till date, is best known for

facilitating the integrated design. Keeping this in view, continuous efforts are being made in exploring the

possibility of BIM in facilitating the development of green buildings. The usefulness of BIM is widely being

recognized to facilitate the design and construction of green buildings. The innovation of BIM technology in the

field of green and sustainable buildings has brought us some latest means to predict, manage and monitor the

environmental impacts of construction through its virtual prototyping and visualization technology. Due to

integration and coordination of BIM with different models like Mechanical, Electrical and Plumbing (MEP) and

architecture it can enclose lots of information within one single model which helps in efficient analyses of

environmental performances and to enhance sustainability measures more precisely. [5]. BIM is possibly a best

tool to integrate the analogue-energy buildings, the air flow analysis and buildings’ sunshine ecosystems. Using

BIM helps us to reduce the energy consumption and construction waste to a greater extent and improve the quality

of construction [6]. With the availability of innovative software’s like Green Building Studio (GBS) which uses

cloud computing technology for the different analysis of building by gathering data from its nearest weather

station. It can perform task like estimate energy consumptions, production and use of renewable energy, and can

calculate the annual carbon footprint of the building. [5].

The different ways through which the BIM can help in planning and design for building sustainability are as

179


follows:

Check the orientation of building, Analysing the building's massing, Conducting day lighting analysis. Analysing

the water harvesting potential to reduce water requirements. Modelling building energy performance. Check for

the sustainability of materials. Designing site and logistics management. Focusing on ecological maintenance.

Recycling rainwater. Using natural ventilation. [5]

The environmental impacts of construction and demolition works are getting severe after a growing number of

construction activities are noticed. The ever-increasing amount of construction and demolition waste disposal in

landfills has become a serious socio-environmental concern and a political issue. But with the growing awareness

of environmental sustainability, governments and industries are looking towards effective Construction and

Demolition (C&D) waste management practices. For this purpose, practitioners have also been working hard to

create the BIM based tools for estimating the waste from the demolitions of buildings. SMARTWaste is one of

such tools that provide access for estimating and identifying the types and amounts Establishment. The working

of SMARTWaste is based on the use of available regional data and reliable and accurate records of waste produced

[5].

However, due to the lack of knowledge the practice of BIM for the building projects is still quite low due to

limited knowledge about this innovative technology, but its full potential is yet to be discovered by the experts in

the coming years [5].

Sustainable construction’s aspect of waste reduction can be achieved through BIM. [21, 22]. BIM software’s like

Green Building Studio can calculate the amount of renewable energy production through solar and wind and their

feasibility [25, 26, 27]. BIM helps designers and engineers in choosing optimal design scheme balancing carbon

emissions, energy and cost for client through multi objective optimization model. [23]. BIM software’s like green

building studio provide water analysis mainly at design phase by estimating water usage based on relevant factors.

They help in optimizing water distribution system of buildings [25] of waste products that will be generated at

site. This tool is developed by the UK Building Research. The researchers in Pakistan have not still worked on

effects BIM can have on green buildings. This research will build a pathway for new researchers in the field of

BIM and Green Buildings in Pakistan.

3. Research Methodology

The multi-step methodology of this research is same as in other review articles. [9] [10] which is based on the

factors identified from the literature review of several research papers on Green Buildings and BIM [3-6-13-19]

but most of the literature review was based on the relationship of BIM and Green Buildings or Green BIM. From

those academic papers, top 19 papers were identified for the topic of “Benefits of BIM on Green Buildings”. The

20 factors were the top most factors mentioned in previous research papers which are listed in this paper at later

stage in the table with the name of author and year of publication of the paper. Questionnaire was then designed

and propagated among various AEC professionals to sort out the most common benefits of BIM on green

buildings. Average indices were compiled through the Statistical Package for the Social Sciences (SPSS) software.

The results were compiled through the help of pie charts using MS Excel too. In the end, trials were done on

Green Buildings Studio for a model building to validate the benefits.

180


Figure 3.1 Flow Chart of Methodology

4. Research Findings

The research findings were than simulated on a software in which a Hospital model was justified on Green

Building Studio. The rates of Electricity and Fuel were entered according to local government rates. Energy and

water analysis were done. The results in table 4.2 show that because of BIM we can make changes in the model

and make the savings up to 4 lac Pakistani rupees per year.

A trial resulted in saving of nearly 11 tons of carbon emission annually which saves fuel and virgin recourses of

a country and help protect our climate by producing less carbon emissions with saving in cost too. The results in

table 4.3 give the comparison of the trails with respect to base run of project which shows the cost of the designed

model without the changes and give the savings of energy, fuel and carbon emissions.

The results enhance that green building are need of time now with the increasing global warming and architecture

and construction industry being big contributor to that as mentioned earlie

181


Table 4.1 Identified Fctors

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Factors of BIM affecting

Green Buildings

2008

2008

2008

2010

2010

2010

2011

2012

2012

2013

2013

2013

2014

2015

201

5

2015

2015

2017 TOTAL

1 lack of computer tools and

the complications of the BIM

models are hindering the

adoption of green BIM.

1 1 1 1 1 1 1 1 8

2 BIM improved building

performance objectives on a

project

1 1 1 1 1 1 6

3 BIM helps in Improving

Energy Efficiency into

project lifecycle

1 1 1 1 1 1 1 1 1 1 10

4 BIM helps in making

sustainable early design

1 1 1 1 1 1 1 1 1 9

182


5 operating costs of green

buildings are

around 14% lower than those

of traditional buildings

1 1 1 1 1 1 6

6 using BIM helps in making

recommendations for design

alternatives that will enhance

a building's performance

1 1 1 1

1 1 1 6

7 Carbon foot printing with

BIM helps us test conceptual

designs so we can specify

solutions with the lowest

carbon impact.

1

1 1 3

8 BIM gives us options that

lead to carbon savings during

a building's operation

1 1

9 Tying BIM to materials can

significantly reduce

construction waste and

streamline the supply chain

through more accurate

procurement.

1

1 1 3

10 BIM helps to quantify the

amount of water used in a

building by calculating the

number of fixtures (sinks,

toilets, etc.) and their related

water usage

1

1 2

183


11 BIM helps us measure the

potential for greywater

reuse, which is highly

beneficial for reducing

demand on local water

supplies

1

1

12 The amount of water

available for harvesting can

be calculated using BIM,

based on the site, harvesting

system, and the size of

building.

1

1 1 3

13 BIM helps in better design

due to improved

collaboration with the supply

chain and customer,

facilitating green

innovations.

1

1 1 1 1 5

14 BIM helps us in improving

facility management and

enabling the verification and

improvement of the

building’s environmental

performance

1

1 1 1 1 1 6

15 Green Buildings lower life

cycle cost and environmental

impact of the building

through its construction and

operational phase delivering

enhanced asset value

1

1 1 3

16 Green Buildings improve

indoor conditions such as

climate and lighting, driving

improved occupant well-

being and productivity.

1

1 1 1 4

184


17 Using BIM Lowers material

wastage and improved

hauling during construction

due to better project

definition

1

1 1 3

18 Using BIM with different

software’s we can know

about the potential green

energy production of the

projects during the design.

1 1 1 1 4

19 BIM tells us about the

energy, water, fuel usages

and tells the yearly and

lifecycle cost of all these

1 1 2

20 BIM provides a means for

modelling the impacts of

facility management by

promoting, sustainable build

environment by using multi-

dimensional visualising

technology.

1

1 1 1 1 1 1 1 8

]

185


Table 4.2 Trials on Green Buildings Studio

186


Table 4.3 Results with comparison of base run

187


5. Results

The results show that BIM has accomplished itself as the best technique in the construction of green buildings.

BIM is very helpful in early design stages in Energy and Water analysis of a construction project. BIM also aids

in reducing carbon emissions of project and lifecycle cost of the project. Following are top thirteen properties of

BIM that benefit the BIM in Green Building construction. These were ranked according to the research conducted

through questionnaire and results generated through SPSS. The Cronbach’s alpha for the results was 0.825 which

is more than 0.75 and satisfactory for results.

i) BIM in integration with software’s like green building studio, can simulate and optimize energy

efficiency of every part of building from energy use to interior climate.

ii) BIM helps in making sustainable early design.

iii) With the help of Green BIM project stakeholders can make early decisions in the design phase.

iv) Green BIM influences the efficiency and working of construction project.

v) Green Building have greater asset value because of its lower lifecycle cost and environmental

impact of the building through its construction and operational phase.

vi) Energy Efficiency can be evaluated by using BIM in design process.

vii) Using BIM helps in making recommendations for design alternatives that will enhance a building's

performance.

viii) Green Buildings improve occupants living by improving indoor conditions such as lighting and

environment of building.

ix) BIM improves buildings environmental performance by improving facility management.

x) Better innovative green designs can be achieved with help of BIM by improving collaboration with

the supply chain and customers.

xi) Waste of material is reduced during construction by using BIM due to improved project

representation and improved transportation of material.

xii) BIM helps in reducing construction waste significantly and streamline the supply chain through

more accurate procurement.

xiii) BIM tells us about the energy, water, fuel usages and tells the yearly and lifecycle cost of these.

6. Conclusions and Future Research

The BIM has proved itself in green building construction industry and it is very effective. Although the use of

BIM is more in early design stage and it gives the best results in this stage because of changes that can be made

after different alternative trials through Green Building Studio and implementing the one which gives the best

results. These softwares integrated with BIM give the yearly and lifecycle cost of energy and carbon emission of

project but is less concerned in construction and demolition phase of the project. There is no any reliable software

to calculate the carbon emission and energy use during design phase including the material which is brought to

site which also consumes energy. There should be an application which can be used for these analyses at

retrofitting and demolition phase of a structure. The software should also include the function of reduce, reuse

and recycle of the waste before the demolition phase has started. It should give choice of construction with less

and recycled material.

References

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[2]. https://www.usgbc.org/articles/green-building-facts

[3]. Yujie Lua, Zhilei Wub, Ruidong Changa, Yongkui Lib, Building Information Modelling (BIM) for green

buildings: A critical review and future directions. Automation in Construction 83 (2017) 134–148.

[4]. Building Information Modeling For Green and Energy Efficient Buildings Design, Nuthan Dummenahally

1 PhD Student, Department of Structural Engineering, Poznan University of Technology, Poznan, Poland 1

[5]. Enhancing environmental sustainability over building life cycles through green BIM: A review Johnny

KwokWai Wong, Jason Zhou

[6]. Wojciech Bonenberg, Xia Wei, Green BIM in sustainable infrastructure. Procedia Manufacturing 3 (2015)

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N. Dawood, M. Kassem (Eds.), Proceedings of the 13th International Conference on Construction

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189


Iron Oxide Modified Zeolite from Coal Power Plant Ash for

Pollutant Treatment – A review

Muzamil Hussain Memon, Suhail A. Soomro, Shaheen Aziz, Uzair A. Kolachi

Chemical Engineering Department, Mehran University of Engineering & Technology, Jamshoro, Sindh Pakistan 76062.

Abstract

In the last few decades, the synthesis of iron oxide modified zeolite (IMOZ) had acquired much attention of

the researchers. Zeolite can be synthesized from a number of resources that may contain alumina-silicate

substance; ranging from clays to waste material from different activities. Coal fly ash is one of such resource;

rich in microspores aluminum-silicate for zeolite synthesis. Furthermore, IMOZ has, however, high surface

area, unique pore characteristics, and excellent ion exchange capacity. The modification of zeolite with iron

oxide increases the capacity and capability of removing pollutants mainly caused by agriculture, domestic and

industrial activities. It is also used for elimination of ionic species (viz., nitrate, phosphate, ammonium, sulfate,

fluoride, and chloride) and heavy metals (viz., mn, w, cr, cd, cu, sr, fe, pb, ni, as, zn, cs, and hg) from waste-

water from domestic, industrial waste, streams’ water, and acid mine drainage. In addition, the iron oxide-

zeolites novel application as sorbent medium in reactive permeable barriers and pollutant barrier inside layer

for the pollutant immobilization. In this article, literature has been reviewed for the synthesis and application

of IOMZ.

© 2018 Muzamil Hussain Memon, Suhail A. Soomro, Shaheen Aziz, Uzair A. Kolachi Selection and/or peer-review under responsibility

of Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro,

Pakistan.

Keywords: “iron oxide modified zeolite, removal of heavy metal and ionic species, pollutants treatment, applications, coal fly ash, power plant;”

1. Introduction

Mineral coal is one of the minerals which is most important and available evenly in abundant quantity in the

entire globe. Its proven world-wide reserves are nearly one trillion tons. Many countries of the country fulfill

their electricity requirement through coal power plants such as like, the United States {49%}, China {79%},

Poland {92%}, and South Africa {93%} [1]. The main serious problems in the coal power plant are the

production of coal ash which is about its 30% by weight [2]. Almost all coal fly ash is discarded in a landfill

as a waste which is costly and contributes to environmental pollution as well. Therefore, it is a dire need to

focus on the coal fly ash (CFA) utilization. Fly ash (FA) is left-over generated from coal power plants in bulk

quantity [3]. Because of its availability and inexpensive its demand has got pace during since a couple of

decades and it has been used in brick industry [4], in cement industry, as a reinforcing filler in polymers [5].

Besides this CFA is also used for the synthesis of zeolite, silica aerogel has great content of alumina and silica

[6]. Zeolites are natural occurring comb-like sponge material with 3-dimension tetrahedral structure. One of

its unique properties is that it possesses negative on it which makes zeolite unique and huge range of

applications. The formula of a zeolite is F2/mO.Al2O3.aSiO2.bH2O, where F is an alkaline earth element or

alkali, m, is the valence charge on that element, varies from {2 – 11} and b vary from {2 – 8}. Zeolite can also

be synthesized from other resources such as fly ash, biomass, kaolin, slag, and other raw materials.

* Corresponding author. Tel.: +92-315-39869-77.


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Naturally occurring zeolites have limitation to their pore size and channels because of that they have limited

scope and applications, however, synthetic zeolite from fly ash possess a variety of pores and channels hence

it is economically suitable for trapping different contaminants from water and air [7], also as shown Table 1

zeolite types. It has been reported that zeolite fly ash has high sorption’s capacities than fly ash (5-8 times) and

ordinary zeolites (2-6 times) [8].In former studies, it has been acknowledged that iron-oxides have a very high

affinities for pollution present in water. For zero emission, a new method has been developed in which

synthesizing of ZFA/hydrated iron oxide modified zeolite from CFA. In this method neutralization of the waste

alkaline-solution with soluble iron salt to formation ordinary ZFA. This method eliminates not only waste of

alkaline solution but also possesses the high capability for pollutant reduction. In a previous couple of decades

iron oxide has proved for discarding pollutants (anionic); phosphate [11], selenite [10], and arsenates [9] from

contaminated waters.

Table 1 some common zeolites synthesized from fly ash (Koshy et at., 2014)

Zeolite Type Chemical Formula References

Analcime NaAlSi2O6·H2O. Remy and Ferrell (1989)

Cancrinite Na6Ca2Al6Si6O24(CO3)2·2H2O Qiu and Zheng, 2009

Clinoptilolite (Na,K,Ca)2-3Al3(Al,Si)2Si13O36·12H2O Zabochnicka-Świątek and Malińska (2010)

Hydroxy-sodalite Na1.08Al2Si1.68O7.44·1.8H2O Ahmaruzzaman (2010)

Mordenite (Ca, Na2, K2)Al2Si10O24·7H2O Sasaki et al. (2003)

Phillipsite (Ca,Na2,K2)3Al6Si10O32·12H2O Hay (1966)

Na-A Na12Al12Si12O48·24H2O Qiu and Zheng, 2009

Na-P1 Na6Al4Si4O24·4H2O Qiu and Zheng, 2009

Na-Y Na58Al58Si134O384·260H2O Qiu and Zheng, 2009

Na-X NaAlSi1.23O4.46·3.07H2O Ahmaruzzaman (2010)

Scolecite Ca2Al2Si3O10·3H2O Qiu and Zheng, 2009

2. Synthesis of Zeolite & Iron Oxide Zeolite

2.1 Coal Power Plant Ash to Zeolites

Fly ash activation was carried out by basic chemicals like NaOH, KOH, CaOH2 and LiOH, experiences

dissociation and followed by crystallizes into zeolitic minerals. There are several synthesis processes/ methods

such as (i) alkali fusion-assisted hydrothermal treatment [19-25], (ii) conventional refluxing method, (iii)

molten salt method [34, 35], (iv) conventional hydrothermal treatment [6-18], (v) ultra-sonication-assisted

hydrothermal [28-32] and (vi) microwave-assisted hydrothermal treatment [26, 27], as shown Fig. 1. Instead

Syn

thes

is o

f Z

eoli

te M

eth

od

s

Conventional Hydrothermal Treatment

Ultra-sonication-Assisted Hydrothermal

Alkali Fusion-Assisted Hydrothermal Treatment

Microwave-Assisted Hydrothermal Treatment

Molten Salt Method

Conventional Refluxing Method

Fig. 1. Synthesis of Zeolite using different techniques

191


of these, alkali leaching of FA is another technique to synthesize pure zeolite from alumina and silica. Particle

size of the original FA decreases due to basic etching on the FA particles surface and followed by nucleation

and crystallizations zeolite patterns minerals, also change in composition FA to zeolite and iron oxide zeolite

as shown in (Fig. 2 and 3) and Table 2, at the end an increase in specific surface area witnesses [36-39].

As a result, this increment in surface-area assists improved sorption’s physical characterize in the final material.

The synthesis of zeolite makes contaminant sorption’s capacity limited due to the abundant quantity of residue

of fly ash present [38]. Hence, it is compulsory to pretreat raw FA to achieve pure zeolites. In fly ash large

particle fractions >252 µm, carbon un-burnt is currently liable on the types of coal and firing system which

can be avoided by employing screening so as to increase zeolization potential, end in a higher surface area

[39,42]. In addition to this, cal-cinations at high temp. (800 ±1 ºC) can eliminate unburnt volatile and carbon

components. More ever, the removal of Fe2O3 and TiO2 with the help of magnetic separation technique

improves purity and structure of zeolites final product.

Quite interestingly it has been observed that the zeolites surface loaded with iron and titanium species to

enhance their cation exchange capacity [43]. By washing (water) of fly ash can reduce the concentration of

soluble molecules/ compounds Na2O, MgO, CaO and K2O [44] and decreases the pH (which is initially >10).

Instead of this, acid treatment removing impurities from the fly ash like ferric oxide and yields a higher

concentration of alumina-silicates [44, 45]. Furthermore zeolites can be prepared using with solution (NaCl)

treated to achieve saturated zeolite cation which differs better ion exchange capacity [38].

2.2 Modification of Zeolite to Iron Oxide Zeolite

Formation of iron oxide zeolite (ZFA/Fe2O3) composite, using different molar solution of (0.66 to .87) M an-

hydrous Fe (III) chloride (FeCl3), hex hydrate iron chloride and another form was added drop wise with stirring

constant, into the combination of waste alkalines material and after process ZFA cool down to normal

temperature at hydro-thermal process. Fe (III) chloride added equally to NaOH solution used in zeolite

preparation. The solution is sufficient for the process of Fe (III) chloride through an alkaline solution, after

addition of Fe (III) chloride material where mixing continually for 4 hours. The ZFA/Fe2O3 combined

compound was then recovered, wash, drying, and powdered. Another method for formation of iron oxide

zeolite is primarily, it was submerged in demineralize water use for 26 hours to decrease its alkali-scenic, and

drying it normal temperature. Natural zeolite sample 0.1 kg was transmitted to a flask-ware container where

2.0 M NaCl solution with 1 L of demin water. The material was mixing for 24 hours at normal temperature

and decantation was used to separate the phases. The sample was washing through demineralized water until

the removal of Cl ions was succeeded, for test chloride ion used with AgNO3 silver nitrate. At the end, zeolite

(NaZ) was treated with sodium and air-dried. Iron-hydro (oxide) modified-zeolite (IHOMZ) synthesized

through, 50 g of NaZ was shifted into a flask holding 500 mL of Fe (NO3) 0.5 molar concentration used, and

the solution pH was adjusted to 3 and 4 using NaOH 0.1 molar concentration and HNO3 0.1 molar concentration

Fig. 2. XRD pattern show crystalline phase peaks fly to zeolite synthesis

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used. The material was shake at 160 rpm for 24 hours., the solid phase has been separated then was washed 2

to 3-time with demin water and dried in open air [47].

CFA treated with alkaline solution where ZFA compound content was changed as show in Table 2. The IOCZ

was prepared in two stages: press oxide planning, trailed by covering iron oxides on the purchased zeolite.

Initial, 200 mL of FeCl3 arrangement was included NaOH with 10 molar concentration at 185 ml arrangement

through dribbling gradually; subsequent precipitates were washed and flushed with demineralize water for 4 or

5 times, and afterward dried in a broiler of 115 for 24 hours; dried iron oxide powder was used consecutively

with demineralize water to rehydrate mud with 46% dampness. Additional, every 50 g of UMZ was blended

with 5 g of mud (iron oxide), and kept the mud being consistently covered on the surface of UMZ; the

subsequent zeolites were then dried at 110 0C for 20 hours, chilled off to filter and discharged with demineralize

water until no pitifully related iron oxides were discharged and also cool down at room temperature. [38].

Table 2 CFA to ZFA & ZFA/ Fe2O3 impact in composition (Xie et al., 2014)

CFA ZFA ZFA/Fe2O3

Fe2O3 2.90 2.77 25.39

Al2O3 38.05 34.19 21.07

MgO 0.67 0.75 0.39

SiO2 48.00 38.67 32.99

CaO 2.32 2.42 0.55

TiO2 1.64 1.34 0.80

Moisture 0.25 6.32 9.10

Na2O 0.47 8.41 3.80

LOI 3.18 4.17 4.55

Other 2.27 0.99 1.34

3. Application of Zeolite & Iron oxide zeolite for pollutant removal

In sole solution or mixed matrix by iron-oxide coated zeolite, IOCZ and unmodified zeolite UMZ the pollutant

including phosphate, sulfide, and ammonium, in batch testing should be detached. The oxidation abiotic of

ammonia is very difficult at the room temperature if there is not the sufficient quantity of microorganisms

available same as herein, catalysis such like as photo-oxidize the ammonia have been exposed using titanium

dioxides [44]. It was discovered that iron-oxides coated a little threatened the subtraction of ammonium but

greatly increased sulfides and phosphates are subtraction in the solution. The pollutant reduction was slow to

process, and normally it took couples of hours or even more to get equilibrium. Therefore, especially for the

removal of phosphate and sulfide some irreversible surface chemical processes like precipitation should be

developed [49].

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3.1 Phosphorus and Ammonia

The treatment of wastewater was recommended to use zeolite for phosphorus and elimination of ammonia by

zeolite and modified zeolite [51], however, a small number of pollutant are removed by zeolite and modified

zeolite, as concluded by the earlier study (0.124 mg/l) , [52]. Though, IOCZ exhibited a higher phosphate

reduction bulk than UMZ with a considerable increase from 0.1191 to 1.009 mg/Pg. As determined by [53],

for effective removal of phosphates the coated iron oxide considered suitable to be used while the phosphate

requisitioning capacity of IOCZ discovered to be less than those as researchers found in many kinds of literature

[54]. For the determination of the IOCZ removal capability for these contaminants, consistent sorption

isotherms on IOCZ and UMZ were also analyzed which are given in Fig. 2.

The simulation of the data was performed with Freundlich and Langmuir equations, and the conforming

parameters. Both IOCZ and UMZ were found having a good sorption capacity with ammonia, while the coated

iron oxides did not greatly affect the ammonia sorption capacities, as their Langmuir maximum sorption

capacity were almost the same (6.78mg/g for IOCZ vs. 7.02 mg/g for UMZ). Though, the sorption isotherms

exposed the IOCZ seems to sorb slightly more ammonia than UMZ under the same concentrations. The minor

variance could be recognized to a smaller amount BET surface (16.02 m2/g for IOCZ vs. 19.7 g for UMZ), as

well as the higher pHpzc on IOCZ, which were expected to attract a less negative charge. The ammonia sorption

by zeolite was usually studied, and the sorption volumes naturally ranged b/w about 4 and 28 mg/Ng [57], in

which the NH4 sorption on UMZ in this study fit.

3.2 Sulfides and Arsenic

In some previous studies found that the less quantity around (0.832 mg/kg) of sulfides can be isolated by UMZ,

but the sulfide separation capacity of IOCZ enhanced to 17.859 mg/kg. Consequently, the iron oxides coated

can rise sulfide elimination, as high-lighted in the former studies [59]. The ammonia elimination was originally

withdrawn by sulfides and also overdue phosphate elimination. Though, these parallel anions appear not to

distress the final separate elimination. Founded on the calculated the simultaneous anions, specifically

phosphates, may enhance the ammonia adsorption capacity on IOCZ. The sequestrated phosphates were mostly

attributed to the increase in the negative charges on the surface of IOCZ. The iron oxides coated through the

process slow in first 14 hours besides this, it greatly promotes the anionic chromate removal, and the IOCZ

was discovered to have a high capacity to illuminate cationic heavy metals. Fe(III) in iron (hydro) oxides may

be compact by the sulfide solution into Fe(II), and sulfide intervening time can be removed by the conversion

from S(II) into S(I)/S(0).

Succeeding, to form precipitates of FeS or FeS2 the Fe(II) obtained can react with the mono-sulfide or more

sulfide . It was considered that the ferri-hydrite as the utmost reactive iron oxides to eliminate sulfides, and it

was found that its conversion to a more crystalline mineral with the aging disfavored the sulfide retardation

[58]. The absorption characteristics of arsenic (As (V)) on iron-coated zeolite (ICZ) were analyzed through

batch and column studies. As (V) was totally illuminated within 30 min in a conc. of 3 mg/l, with a 170 g/l

dose of ICZ. The optimum dose of ICZ was 66.6 g/l at a conc. of 33.24 mg/l and the effect of solution pH was

insignificant at a pH range of 2.1 < pH < 11.1. The sorption characteristics of As (V) were befitting to explain

onto ICZ Langmuir Isotherm Model. The co-existence of ions (sulfate) prevented absorption of As (V) because

of competitive adsorption. The absorption capacity of ICZ for As (V) was 1 mg/g. Based on the outcome, ICZ

is an appropriate material to treat the wastewater or mine drainage bearing As (V) [60].

3.3 Vanadium

Vanadium has a strong liking to various components present in soil like organic materials, clays, and iron

oxides, and can be ascribed as relatively immovable in soils, sediments, and mine tailings. There is no specific

legislature about the vanadium perimeter values because there is no high level of vanadium present in natural

waters, except in a few countries. In China, there is a limitation of 60 µg/l present in surface drinking water

sources while Italy has 145 µg/l for underground water. As Vanadium pentoxide is investigated and found

perhaps carcinogenic to humans, so the concerns for vanadium removal from water have been multiplied. There

are several proven chemical techniques to eliminate vanadium from the water. Vanadium presents mostly in

194


its oxidation state +6 in aqueous solution if oxygen is present in solution. V (V) presents as an anionic species

when the pH is higher than ~4. Polynuclear V (V) kind has high concentration whereas mono-vanadate species

exist at lower concentration (~2.6 mg/l). Thus, vanadate for anion exchange has been used effectively.

Pertaining to water humic substances may hold vanadate and the framed edifices shaped may demonstrate

different affinities to the desorption localities. More ever, humid matters contend with vanadate for the sorption

locales. This investigation was deflected the vanadium expulsion from common water gathered from the region

of the Mustavaara vanadium pit in Taivalkoski, north-eastern Finland. Vanadium starts from the V-Fe-Ti store

of the mine site. The principal objective was to look at the productivity of sorption strategies and conjunction

with an iron coagulant. Alkylammonium-functionalized clinoptilolite (Cp) and engineered Na-zeolite-P1, got

from fly slag [19] and additionally, ground ferric oxy-hydroxide (CFH-12) were chosen as adsorbents. Every

one of these materials had been already tried for vanadium expulsion from model arrangements, nonetheless,

not from normal water. The point of the nitty gritty portrayal of crisp and utilized sorbents were to give

understanding of the systems in charge of vanadium take-up. In the co-precipitation tests, a business ferric

sulfate coagulant (PIX-322) was utilized. Furthermore, synchronous adsorption on co-precipitation with iron

(III) and organ-zeolite salt was researched. The iron coagulant is a viable accuse neutralize and responds of the

humic substances of in regular water, by shaping settle-able flocs. At the same time, joining vanadium species

to unsolvable flocs or iron species respond positively.

4. Permeable Barriers

The contaminants such as hazardous and leachates compound in soil penetrate due to rain-water percolation,

because of this both the groundwater and surface water became contaminated [64]. In this sense, permeable

reactive barriers (PRBs) propose in-situ re-mediation at less maintenance charge and less operate [63].The

concept of PRB for treatments of an impurity plume in the soil as shown in Fig 4. PRB is reactive media similar

IOMZ exchange resin, and activated charcoal should have a hydraulics conductivity more than surrounding of

media, e.g., In order the soils, to let the stream flow of the impurity plume throughout the underneath barrier

is ordinary hydraulics grade [62]. Quite interestingly, a soil iron oxide modified zeolite (IMOZ) a technique

called layers has also been consumed for the treatment of contaminated canal water and also this technique has

the potential to be improved via FA base zeolites. [64]. Have proposed that in an FA zeolite PRB with gate and

funnel configuration (a system of walls which channelize the impurity plume in the direction of the PRB), a

subordinate electro-kinetic treat, also it is providing subsequently the treat through the PRB has been finished,

can be engaged for confirming impurity elimination completely.

Fig. 3. Schematic diagram of a permeable reactive barrier (PRB) (Koshy et al., 2014)

195


5. Conclusions

Iron oxide modified zeolite (IOMZ) have been represented comprehensively in writing to be a viable scavenger

of harmful or dangerous anions and cations in water. Notwithstanding this, they have the ability in effluent

treatment for evacuation of light and overwhelming metals toxins and for applications, for example, penetrable

receptive obstructions. The toxin expulsion by utilizing IOMZ happens through desorption as well as

precipitation and the evacuation effectiveness relies on the underlying contaminant fixation and the strong to

the fluid proportion of the framework. Just a couple of studies have been directed on the expulsion of mercury

and arsenic by using iron oxide changed zeolite. Bacterial stacking on FAZ can be utilized for phosphate and

substantial metal expulsion, in this manner offers, a financially practical option in contrast to existing

techniques. In spite of the fact that reviews exist for landfill leachate treatment utilizing crude FA remains,

usage of FA-based zeolites could yield better outcomes as found by a couple of past research studies. While

countless have been led on overwhelming metal evacuation, not many investigations exist on other vital

applications, for example, soil remediation utilizing porous responsive hindrances (PRBs). Despite the

examinations on PRBs using the regular and business zeolites, utilizing of fly powder-based zeolites has not

been found much. For regulation of dangerous, radioactive waste and lethal, the achievability of liner materials

utilizing settled fly fiery debris zeolites can be resolved. Encourage more, in situ-remediation studies, would

be very valuable to comprehend the viability of this material in expansive level asset recuperation innovations.

6. Acknowledgments

The authors would like to acknowledge the department of Chemical Engineering, Mehran University of Engineering & Technology for proving laboratory facilities & financial support. The British Council & Higher Education Commission Pakistan is also acknowledged for supporting the Pak-UK Knowledge Economy partnership project for the Utilization of Nagarparker Kaolin to Zeolite.

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198


Impact of Total Quality Management (TQM) Practices on

Sustainable Development

Asif Nawaz, Muhammad Saad Memon*, Sonia Irshad Mari, Miskeen Ali Gopang

Dept. of Industrial Engineering and Management, Mehran University of Engineering and Technology, Jamshoro, Pakistan

Abstract

The aim of this paper is to analyze the impact of total quality management (TQM) practices on the sustainable

performance of manufacturing industries. This study develops an integrated framework to analyze the relationship

between TQM and sustainable practices. An exploratory factor analysis was conducted to analyze the significance of

various TQM practices and their impact on sustainable performance. The findings revealed that the total quality

management and sustainable development are the most important approaches in the success of manufacturing industries.

From the findings, the study suggested the manufacturing industries should improve their quality management programs

and sustainable performance for the success of the company. The results generated the structure of the TQM and

sustainable development framework based on the major practice of the total quality management and sustainable

performance which helps in the success of the companies.

© 2018 “Asif Nawaz, Muhammad Saad Memon, Sonia Irshad Mari, Miskeen Ali Gopang” Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: Total quality management (TQM), Sustainable development, sustainable performance, exploratory factor

analysis

1. Introduction

Quality is the considered a key factor in achieving the success of the business and it is more than ever important for

competing successfully in today’s worldwide market position [1]. Now a day’s quality management must play a major

role in the development of the business. Quality is a compulsory component in the production of goods and services for

the satisfaction of the customers. Quality is defined as circumstances that meet the needs of the customers, which is

measurable and achievable [2,3]. Total quality management is a firm-wide management thinking of continually

improving the quality of products by the focusing on the needs of the customer’s and their expectations to enhance the

satisfaction of the customers and firm performance [4]. Total Quality Management (TQM) is a process started by top

upper management to attain the involvement of employees in the continuous improvement of the performance of all

movement in the organization [5]. Total quality management is the finest way of running an organization to achieve

excellence. Total means everything in organization and quality means in the degree of excellence. Sustainable

development is the managing principle for convention human development aim while at similar time sustaining the

ability of natural systems to provide the natural resources and ecosystem service upon which economy and society

depend. TQM is considered the main aspect of the organization's success. To achieve sustainability goals, the three

aspects of the triple bottom line must be harmonized, integrated and balanced effectively [6]. The purpose of this study

is to determine the key practices of total quality management and their impact on Sustainable development. The aim of

* Corresponding author. Tel.: +92-333-2888606.


199


this study is to analyze the implementation of TQM, and its impacts on sustainable practices. Based on the objectives of

the study, the following are the research questions:

1) Which practices of Total Quality Management are found to have the highest impact on sustainable development?

2) Is there is any relationship between TQM practices and sustainable development?

2. Literature Review

TQM has since the 1980s, become a worldwide management focus. The line of total quality management can be outlined

back to the early 1920s. The focus extended from quality of products to the quality of all issues within an organization

[7]. Total quality management is generally considered as a collective organization path for improving the quality of the

product and quality of the service [8]. The TQM focus on improved economic sustainability constitutes one area of

potential synergy [9]. Total Quality Management (TQM) is a concept designed to continuously improve the processes

of an organization as part of the management’s system [10]. The origin of the English word sustain is in the Latin words

sub (under, from below), and tenere (to hold, to hold up). To sustain, then, means to keep up, to maintain, to support, to

prevent from sinking or falling something. Sustainability is the ability to maintain or support an activity or process over

the long term [11]. TQM practices have positive relations with organizational performance [12]. Design optimization,

process optimization and product or service reliability by themselves are sources of quality advantage [13]. TQM is a

customer-focused approach aimed at meeting or exceeding customer expectations with regard to products or services

[14]. There are many perspectives and definitions of quality, which are supported by philosophical frameworks

developed in the past including Deming, Juran, and Crosby [17]. For many years, sustainable development was viewed

as irrelevant for benefit producing business. Traditional production organizations are starting to comprehend and seek

an after a corporate objective of sustainable development. While the term sustainable development is some degree

confusing and indefinable to production organization. Sustainable development is defined as that meets the requirements

of the present generation without compromising the ability of future generations to meet their own needs [18]. In

development of quality activities organizations have focusing on sustainability as mean of organizational development

in terms of organizations strategy [19]. The sustainable development gives a framework under which networks can

utilize assets effectively, make proficient infrastructures, protect and increase the quality of life, and make new

organizations to strengthen economies [20]. Sustainability is the considered one of the most important aspect in

determining growth and development. “Sustainability may be defined as sustaining excellently after a long, perhaps

even an indefinite period” and it is broadly measured one of the most important parts in the growth of the organization

[21]. Sustainable development generally consists of the three main pillars of sustainable development, environmental,

and socially sustainable development.There is a positive relationship between sustainable practices and better

performance of a company [22]. The association between TQM and organizational performance was studied by [23,24].

Table 1. Comparing earlier frameworks of TQM practices and sustainable practices

Research study TQM practices Sustainable development

practices

Area

Nguyen et

al.,(2018)

[21]

Top management

Commitment

Training &

Development

Service design

Process mgt:

Cont: improvement

Rewards

Economic performance

Social performance

Environmental

performance

Vietnam based enterprises

Khoja (2016)

[20]

Training

Process management

Customer focus

Leadership

Continuous

improvement

Creativity

Innovation

Recycling neutralizing

Biodiversity

Culture

Ethics

Libyan Higher Education

System

200


Stakeholders

Harm material

Monday et

al,(2015)

[9]

Top Management

Commitment

Strategic planning

Customer focus

Employee involvement

Process management

Innovation

Poverty

Health

Land use

Biodiversity

Productivity

Oil and gas industries in

Nigeria

Mishra & Napier

(2015) [22]

Customer focus

empowerment

Team-based approach

Continuous

improvement

Communication and

Feedback

Environmental focus

Recycling

Disposal

Reuse

Process design

Enhancement of

awareness

Corrective action

Environment of organizations

Kaczmarski (2014)

[15]

Management

commitment

Work environment

change

Training and education

Continuous

improvement

Employee satisfaction

Stakeholders

Triple bottom line

Strategic management

Innovation and learning

Global organizations

E.P.O (2014)

[6]

Continuous

improvement

Teamwork

Change of culture

Total involvement

Training customer

focus

Environmental sustainable

development

Desertification

Environmental pollution in

organizations in Nigeria

Elhuni & Ahmad

(2014) [25]

Customer focus

Continuous

improvement

Top management

Commitment

Vision

Customer focus

Training & education

Process control

Information

technology

Social performance


Environmental

performance

Oil sector

Issakon (2006)

[23]

Top management

Commitment

Focus on the process

Continuous

improvement

Benchmarking

Process management

Employee focus

Stakeholder


Lifecycle

Environmental

performance

Social performance

Manufacturing organizations

Zairi & Ashari Customer satisfaction Sustainable performance Market-based

201


[17] Customer orientation

Management

Commitment

Knowledge Learning

Market advancement

Customer satisfaction

Market orientation

Quality orientation

Revenue growth

This table shows the past studies related with the relationship between Total quality management and sustainable

development and their practices with the area of study. But this study shows these practices Top Management

Commitment, Customer focus Employee Focus Leadership, Continuous improvement Compensation Benchmarking,

Customer Satisfaction, Customer Relations, Service Quality, Training & Education, Employee involvement, Employee

Encourage are the important practices of TQM and cost management, research and development, limited

landfilling,pollution,lifecycle, resource consumption, public welfare,industrial health and safet, stakeholder trust are the

important factors of sustainable development in the manufacturing industries .

Fig. 1 . Factors of sustainable development

3. TQM Practices

The identification of factors affecting the successful total quality management implementation has recently come into

view as a significant research course [8,4,9]. The core theory of TQM has been developed from the leaders of quality

and examined the relationship between total quality management and performance [23,24]. Seventy-eight items were

studied, that was set into eight important total quality management practices [25]. Leadership, , employee management,

quality planning, , process management, customer orientation, , information, supplier management are general practices

which help with successful TQM implementation concern for the society and natural environment [26].Strategic quality

management, Top management commitment , process quality, training and education, benchmarking ,design quality

management, statistical process control are nine TQM practices developed by [27]. They all shared practices of

Leadership, Continuous improvement, Compensation Benchmarking Customer Satisfaction, Customer Relations

Service Quality Training & Education Employee Involvement Cost Management Research & Development Limited

Land Filing Pollution Life Cycle Resource Consumption Public Welfare Industrial Health & Safety Stakeholder Trust.

SOCIAL SUSTAINABLE

DEVELOPMENT

ENVIRONMENTAL

SUSTAINABEL DEVELOPMENT

ECONOMIC SUSTAINABELE DEVELOPMENT

SUSTAINABLE

DEVELOPMENTT

202


Table 2. TQM and sustainable development practices defined by earlier literature

FACTORS SUBFACTORS AUTHORS

TQM practices

Top management

commitment

Leadership Damen,2017, Sadikoglu & Olcay,2013,

Ibrahim,2013, Tayeb,2008, Salaheldin,2009,

Feng et al,2006, Arshida & Agil,2013, Sila,2006,

Ahmad,2014, Khoja, 2016

Continuous

improvement

Fish,2015, Ukwuom et al,2014, Ibrahim,2013,

Lizarell,2016, Salaheldin, 2009, Khoja,2016,

Damen,2017, Cetindere et al,2015

Compensation

benchmarking

Behra & Gundersen (2001), Fish,2015,

Sila,2006, Milovanović,2014, Elhuni &

Ahmad,2014, WANJIKU,2015, Kasongo &

Moono,2010

Customer

Focus

Customer

Satisfaction

Ibrahim,2013, Fish,2015, Sila,2006, Lau&

Idris,2001, Damen, 2017, Zhang et al. (2000),

Customer

Relations

Zhang et al. (2000), Saraph et al. (1989), Sila &

Ebrahimpour (2002), Quazi et al. (1998)

Service Quality

Leppävaara,2012, Jørgensen & Nielsen,2013,

Ahmadabadi,et al ,2012

Employee Focus

Training&

Education

Sadikoglu & Olcay,2013, Ukwuom et al, 2014,

MAINA,2013, Gul et al,2012, McLean,2015,

Hoang,et al 2010, Sila,2006 , Milovanović,2014,

Elhuni & Ahmad,2014Idris,2011

Employee

involvement

Damen,2017,McLean,2015, Hoang,et al 2010,

Salaheldin,2009, Sila,2006, Milovanović,2014, ,

Kasongo & Moono,2010

Employee

Encourage

Wali et al. (2003) , Talib and Rahman

(2010),Salaheldin,2009, Idris,2011,Yusuf et al.

(2007)

Sustainable

development

Economic focus

Cost

Management

Elhuni & Ahmad,2014, Martens&

Carvalho,2016, Rasul & V,2003,

Diaz&Rodriguez,2016, Sebhatu.2008

Research &

Development

Elhuni& Ahmad,2014, Thirupathi &

Vinodh,2016, BASIAGO,1999, Sebhatu.2008,

Amr et al,2016, Tayouga & Gagne,2016

Limited

Landfilling

Amiril,2014, Peña,2015,Elhuni& Ahmad,2014,

Tayouga&Gagne,2016, Amr et al,2016,

Sebhatu,2008

Environment focus

Pollution Peña,2015,Sebhatu,2008, Amiril,2014, Elhuni&

Ahmad,2014, Thirupathi & Vinodh,2016

Life Cycle Amiril, 2014, Elhuni & Ahmad,2014,Diaz &

Rodriguez,2016, Tayouga & Gagne,2016

Resource

Consumption

Alone & Ahmad, 2014, Tayouga & Gagne,

2016,Sebhatu.2008, Amr et al,2016

Social focus

Public Welfare Elhuni&Ahmad,2014,Chen,2016,

Diaz&Rodriguez,2016,Zinik,2007

Industrial Health

& Safety

Martens&Carvalho,2016, Peña,2015,

Amiril,2014, Peña,2015,Elhuni& Ahmad,2014

Stakeholder Trust

Chen,2015, Isaksson,2006, Elhuni &

Ahmad,2014, Amiril,2014, Idris,2011

203


3.1 Relationship between TQM and sustainability

Some studies have supported the notion that TQM and sustainable development have a positive relationship. The total

quality management focus on enhanced economic sustainability constitutes is one part of possible synergy [9].

Primary research indicated that there was a medium to a strong connection between TQM indicators and environmental

indicators.

4. Sustainable Performance

The sustainable performance is idea as an outcome of sustainable organization.Sustainable performance can be

illustrated as “the arrangement of its environmental, economic and social performance”. In this paper, the

sustainable performance is distinct as the reasonable performance among three positions, economic performance,

environmental performance and social performance.

5. Conceptual Model and Research Hypothesis

A literature review shows there is a wide consensus on the importance of TQM practices in the development of a total

quality culture. The conceptual model shows the important practices of total quality management and its effect on the

sustainable development of the organizations. Top Management Commitment, Customer focus Employee Focus

Leadership, Continuous improvement Compensation Benchmarking, Customer Satisfaction, Customer Relations,

Service Quality, Training & Education, Employee involvement, Employee Encourage are the important practices of

TQM.

204


Fig. 2. The conceptual framework of TQM practices and sustainable development

TQM

Sustainable

development

Top

management

commitment

Customer

focus

Employee focus

Economical

focus

Environmenta

l focus

Social focus

Leadership

Continuous

improvement

Compensation

Benchmarking

Customer Satisfaction

Customer Relations

Service Quality

Training & Education

Employee involvement

Employee Encourage

Cost Management

Research & Development

Limited Land filing

Pollution

Life Cycle

Resource Consumption

Public Welfare

Industrial Health & Safety

Stakeholder Trust

205


6. Analytical Framework

In this paper, a framework is produced to demonstrate the connection between Total quality management practices

and sustainable development,also defines the impacts of TQM practices on sustainable development.

Fig. 3. Analytical framework

7. Questionnaire Design and Data Source

In the process of designing questionnaire surveys, the literature analysis was studied to implement the study. First, we

composed questionnaires in the light of literature investigation.

8. Research Methodology

This is a descriptive research study explaining in detail the concepts, theories, and researches to identify the different

TQM practices implemented and their effect on sustainable development. A survey questionnaire method was used to

collect the data. The questionnaire aimed to identify critical success factors of TQM and sustainable development in

manufacturing industries. A total of 250 copies of the questionnaire were distributed to the employees working within

manufacturing industries (Karachi and Hyderabad) Sindh. Five-point Likert scales (strongly disagree, disagree, neutral,

agree, strongly agree) were used in the questionnaire. The questionnaire includes 50 statements to identify critical

success factors for the implementation of TQM.

Independent variables

TQM Practices

Leadership

Continuous improvement Compensation Benchmarking

Customer Satisfaction

Customer Relations Service Quality Training & Education Employee involvement

Employee encourages

Sustainable development

practices

Cost Management

Research & Development

Limited Land filing

Pollution

Life Cycle

Resource Consumption

Public Welfare

Industrial Health & Safety

Stakeholder Trust

Moderating factors

Type of industry

Firm’s size

Dependent variables

206


8.1 Data collection

Data was collected by the extensive literature review. The primary data for the study was collected through the survey

method by using questionnaires. Total 70 responses was collected from manufacturing industries .The Questionnaire

survey was carried out to identify the significant factors and this will be carried out the improving the practices. The

data collected from relevant experts working in different organizations of (Karachi and Hyderabad) Sindh.

8.2 Data Analysis

The data obtained from the data collection methods were analyzed by the use of factor analysis. The data analyzed by

using the Statistical Package for the Social Sciences (SPSS). Descriptive statistics include mean, frequency, standard

deviation and percentages to profile sample characteristics and major patterns from the data.

8.3 Research method

The exploratory factor analysis (EFA) used to find factorial validity. EFA analysis shows accurately what was proposed

to be measured. It is used to identify the structure of the relationship between the variable and respondent.

8.4. Research tools

The results of the collected data were analyzed by SPSS and MS Excel 2013.

9. Results

Out of 250 questionnaires sent to the targeted sample, a total of 70 questionnaires were returned completed. Data

collected were analyzed by using the SPSS programme. The twenty-four practices in the survey were made on the Likert

scale. The 24 items of the questionnaire were intercorrelated and subjected to an exploratory factor examination (EFA)

was led by utilizing SPSS to distinguish the consider structure the variable. Every component of the structure was

deciphered as Likert-scale question.

Table 3. Principle Component Analysis

Initial Extraction

Leadership 1.000 .901

Continuous Improvement 1.000 .946

Comp Benchmarking 1.000 .890

Customer satisfaction 1.000 .977

Customer relations 1.000 .957

Service 1.000 .914

Training 1.000 .931

Involvement 1.000 .956

Encouragement 1.000 .954

Cost management 1.000 .783

Research & development 1.000 .977

Limited landfilling 1.000 .987

Pollution 1.000 .984

Life cycle 1.000 .973

Resource consumption 1.000 .990

Health & safety 1.000 .586

Stakeholder trust 1.000 .981

207


9.2 Factor Extraction

Factor analysis with principal element extraction was performed on the twenty-four administration hones things to

decide the number of components. Other than utilizing the scree plot as a manual to choosing the number of elements

to be extricated.

Table 4. Eigenvalues and % of total variance clarified of TQM and sustainable development

Total Variance Explained

Compone

nt

Initial Eigenvalues

Extraction Sums of Squared

Loadings

Total

% of

Variance

Cumulati

ve % Total

% of

Variance

Cumulative

%

1 10.195 59.971 59.971 10.195 59.971 59.971

2 2.289 13.466 73.438 2.289 13.466 73.438

3 2.047 12.041 85.478 2.047 12.041 85.478

4 1.157 6.805 92.284 1.157 6.805 92.284

5 .947 5.569 97.853

6 .179 1.055 98.908

7 .157 .923 99.831

8 .029 .169 100.000

9 1.130E-15 6.650E-15 100.000

10 4.497E-16 2.645E-15 100.000

11 7.626E-17 4.486E-16 100.000

12 -3.272E-17 -1.925E-16 100.000

13 -5.794E-17 -3.408E-16 100.000

14 -4.424E-16 -2.602E-15 100.000

15 -6.618E-16 -3.893E-15 100.000

16 -8.746E-16 -5.144E-15 100.000

-1.675E-15 -9.851E-15 100.000

208


Extraction Method: Principal Component Analysis.

.

Fig. 3. Using the scree plot as a guide to choose on the number of elements to be extracted

Table 5. Components extracted Component Matrix

Component

1 2 3 4

Leadership .548 -.413 .333 -.565

Cont. Improvement .888 -.002 -.379 -.121

Comp

Benchmarking .575 -.180 .633 .356

Customer

satisfaction .958 -.018 .135 -.203

Customer relations .817 -.400 -.013 .360

Service .928 -.202 .087 .074

Training .954 .044 -.004 .135

Involvement .869 -.095 .265 -.348

Encouragement .952 -.203 -.072 .036

Cost management .438 .120 -.760 -.008

Research&

development .958 -.018 .135 -.203

Limited landfilling .177 .638 .737 .080

Pollution .467 .860 .028 .159

Lifecycle .778 .556 -.133 -.201

Resource

consumption .890 .338 -.102 .272

Health & safety .627 .244 -.321 -.173

Stakeholder trust .780 -.434 -.145 .403

209


According to the column I the continuous improvement, customer satisfaction, customer relations, service quality,

training, employee involvement, employee encouragement are the main practices which have impacts on sustainable

development. The last part of the yield is a relationship matrix among the factor (SPSS). This matrix includes the

correlation coefficient among practices. The results show continuous improvement, customer satisfaction, customer

relations, service quality, training, employee involvement, employee encouragement are the main practices of TQM and

sustainable development which have high value.

10. Discussion and Findings

The study outcomes show that total quality management practices have major impacts on dimensions of sustainable

development. It comes into view that TQM practices have a more considerable impact on environmental, social and

economic performance. A framework was established to find the impact of total quality management practices on

sustainable development. This literature review of the study determines the impact of total quality management practices

on sustainable development and describe the co-relation of TQM and sustainable development practices. The main

practices of total quality management are continuous improvement, customer satisfaction, customer relations, service

quality, training, employee involvement, employee encouragement which has a high impact on the sustainable

development and it is found that these practices have a specific relation to the sustainable development. In summary, it

is obvious that the implementation of total quality management can have surprising advantages to organizations. The

findings also revealed that in the pursuit of sustainable development brings about added value to customers by making

the organizations paying attention to satisfying customer’s needs, while employee involvement and training allow

employees for the continuous improvement of the organization.

11. Conclusion

The past and present study observed that quality could be attained if management is intense and motivates employees

to achieve quality and fulfill the customers for flourishing and business achievement. The conclusions of the study

revealed the importance of the implementation of quality. Total quality management is a continuous process of

incremental improvements. It gives the organization an aggressive edge. This research decides the success practices

essential for the implementation of TQM at different manufacturing industries. A wide review of TQM and sustainable

literature, quality models, and other quality management research results, expose 6 main practices with 18 sub-practices

were defined as a successful practice and considered in the questionnaire. A factor analysis was carried out on the

collected information was used. This helps in to achieve the research questions of our study. The results of the study

visibly show that continuous improvement, customer satisfaction, customer relations, service quality, training, employee

involvement, employee encouragement are the main practices of total quality management which impacts on SD and

also find significant relation on the sustainable development.

12. Acknowledgments

We would like to express our thanks and gratitude for our supervisor for his positive and supportive guidance. Last but

not least I want to thank my family and friends for their support and encouragement.

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a recent WTO member,” Total Qual. Manag. Bus. Excell., vol. 21, no. 9, pp. 931–951, 2010. [5] E. Sadikoglu and H. Olcay, “The effects of total quality management practices on performance and the reasons of and the barriers to TQM

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[6] E.P.O “Total Quality Management for Sustainable Development : A Case of the Nigerian Environment Author ’ s Details :,” no. 5, pp. 1–17, 2014.

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[11] J. A. Dipalma and D. A. Gremse, “Chronic constipation in children: Rational management,” Consultant, vol. 41, no. 13, pp. 1723–1732, 2001.

[12] K. Clement, C. Kasongo, and M. Moono, “Factors that lead to a successful TQM implementation : a Case Study on the Zambian Tourism Industry,” 2010.

[13] Chen, “Sustainability and company performance : Evidence from the manufacturing industry,” 2015.

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[15] M. Jasiulewicz-Kaczmarek, “Is Sustainable Development an Issue for Quality Management?,” Found. Manag., vol. 6, no. 2, 2014.

[16] M. M. Yusr, “Innovation capability and its role in enhancing the relationship between TQM practices and innovation performance,” J. Open

Innov. Technol. Mark. Complex., vol. 2, no. 1, p. 6, 201 [17] M. Idris-Ashar and M. Zairi, “Achieving Sustainable Performance Through TQM and Market Orientation: A Proposed Framework for

Empirical Investigations,” Int. J., vol. 2, no. 2, pp. 1–33, 2004.

[18] M. ul Hassan, A. Mukhtar, S. U. Qureshi, and S. Sharif, “Impact of TQM Practices on Firm ’ s Performance of Pakistan ’ s Manufacturing Organizations,” Int. J. Acad. Res. Bus. Soc. Sci., vol. 2, no. 10, pp. 232–259, 2012.

[19] M. M. Arshida and S. O. Agil, “Critical Success Factors for Total Quality Management Implementation Within the Libyan Iron and Steel

Company,” Iss& Mlb, pp. 254–259, 2013. [20] Mabrouka Khoja “The Development of a Sustainable Quality Management Framework for Libyan Higher Education System This thesis is

submitted in partial fulfilment of the requirements of De Montfort University for the award of Doctor of Philosophy Supervised b,” 2016.

[21] Minh Hue Nguyen 1,2,* ID , Anh Chi Phan 1 and Yoshiki Matsui," Contribution of Quality Management Practices to Sustainability Performance of Vietnamese Firms",Article Sustainability 2018, 10, 375,2018.

[22] R. Mishra and R. Napier, “Linking Sustainability to Quality Management and Firm Performance,” Int. J. Bus. Manag., vol. 10, no. 3, pp. 1–14,

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[24] R. Agrawal and J. Tiwari, “The Integration of Quality Management and Environmental Management - A Review,” pp. 9–13, 2014. [25] R. M. Elhuni and M. M. Ahmad, “An empirical study of TQM and its effect on the organizational sustainability development: A successful

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211

5th International Conference on

Energy, Environment and Sustainable Development 2018 (EESD 2018)

Utilization of Nagarparker Kaolin Purification Plant Waste Material

as Value Added Product

Uzair Ahmed Kolachi, Suhail A. Soomro, Shaheen Aziz, Muzamil H. Memon

Department of Chemical Engineering Mehran University of Engineering & Technology Jamshoro Sindh Pakistan

Abstract

Kaolin is used as an industrial mineral in a wide range of industries. Kaolin is mined from the mining sites & purified

to remove the impurities as per its end use; ranging from the paint industry to ceramics & cosmetics to medical

applications. There is a sufficient quantity of residue is left during the purification process that apparently has no use

and is thrown away. In Nagarparker and Swat, Pakistan, there are huge deposits of Kaolin in Nagarparker, the residue

left is of no use and thrown away near the processing plants. The main focus of the researchers is on the effective

utilization of residue left as waste and converts it into a useful product. Silica Aerogel is one of the products that can be

synthesized from kaolin residue. It is a synthetic porous, light in weight, low density and low thermal conductivity

material produced from silica gel. Due to low chemical reactivity, low thermal conductivity, high surface areas, they

exhibit vast applications in various areas such as the Cherenkov emitters, space science, and super insulating medium.

In the current research, Silica Aerogel was synthesized by employing the sol-gel process. The main focus was on the

impacts of various factors such as calcination, SiO2/Na2CO3 ratios, and alkalinity and aging times.

© 2018 Uzair Ahmed kolachia, Suhail A. Soomrob, Shaheen Azizc, Muzamil H. Memond Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: “Kaolin, waste material, silica gel, aerogel, sol-gel method, adsorbent, value-added product;”

1. Introduction

Kaolin is also known as China Clay. Kaolin is mineral consists of two basic elements “oxides of aluminum and silicate’’

and its molecular formula is (Al2O3-2SiO2-2H2O), and it is derived from Kaolinite mineral comes from the Earth’s Crust.

Historically traces back that it was firstly found in China hence known as China Clay. It is formed by hydrothermal

weathering of feldspar ten to hundred millions of years ago [1,2,3,4]. Pakistan Mineral Development Corporation

explored the kaolin reserves in the period of 1976-1979. Nagar Parker Kaolin reserves were estimated 3.634 million

tons [5], after being carried out number of Bulk Sampling, Physical tests and Chemical analysis [6].

China Clay possesses excellent characteristics such as whiteness, viscosity, chemically inertness and non-abrasiveness.

All these properties make kaolin suitable and widely applicable for variety of applications; some of which are given as,

thermal paper, calcined kaolin, Paper, paints and coating, agricultural, electric wire and cables, plastic and rubber

industry, construction industry [7]. USA had the largest kaolin reserves. Uzbekistan is the second largest contributor of

kaolin and other producers are listed in table.1 given below.

* Corresponding author. Tel.: +92-313-2754664


212

mailto:[email protected]



Table 1. Major Producers of Kaolin in world-2010

Country Production in Thousand Metric Tonnes

United States 5,700

Uzbekistan 5,550

Germany 3,250

Czech Republic 2,950

Brazil 2750

Kaolin found in Pakistan is quite comparable with other countries of the kaolin deposits. The chemical composition of

raw kaolin of Nagar Parkar ranges from 48.7% to 59.2% of silica while ideal content of silica is (46.1%) which is little

higher than ideal one. Silica content is abbreviated to (45.1%) by washing. Similarly, the Alumina content in Pakistani

kaolin ranges between 21.3-26.8%, which is little lower than the ideal one (39.5%). But by washing the raw kaolin, the

Alumina content is increased up to 35.1% which is again closer to the ideal one [6]. Silica gel is an amorphous, porous,

vitreous, granular form of silica dioxide (SiO2) manufactured synthetically from sodium silicate. It is a naturally

occurring mineral which can be processed and optimized into desired shape and size. Silica gel having average size of

24 Armstrong can be utilized as an absorbent. Silica gel possesses unique absorption capability and it can absorb as

much as 40% of its weight. Because of which it can be utilized in numerous applications.

The residue from kaolin purification plant is found rich in silica about 92% which is the most desirable raw material for

the synthesis of silica gel. To prepare silica gel with the utilization of residue from kaolin is most viable and inexpensive

as compared to other raw materials such as rice husk ash, coal ash, by using sol-gel method. The chemical composition

of kaolin residue is 92.72% SiO2, 3.42% Al2O3, 0.71% Fe2O3 and Other oxides. [8]. Silica gel can be manufactured from

other industrial wastes (by-product) such as bagasse ash, husk ash, fly ash which are chief source of silica. The silica

gel obtained from these industrial by-products exhibits variation both in characteristics and properties because the nature

of raw materials depending on the parent industry. [9].

It was studied that precipitated silica obtained from metasilicate solution using HCL. He determined that obtained

precipitated silica has a specific surface area between 120–260 m2/g [10,11]. The effect of pH on the formation of

bimodal porous silica (BPS) from rice husk ash and has a high specific surface area. In this work, efforts had been made

to study the synthesis of silica gel. In order to achieve the objective, various parameters were studied. The parameters

are calcination, ratio of kaolin residue to Na2CO3, behavior of product at various pH value. The product obtained was

determined by employing different analytical techniques such as XRD, FTIR and SEM.

2. Experimental Work

2.1 Separation of Kaolin & by Product from raw Kaolin

In this study the kaolin used was PKR-13, 1kilogram of kaolin was dissolved in two liters of demineralized water under

continuous stirring for an hour. The mixture was then allowed to settle down the course material on bottom of container

and the separation of the top layer of kaolin was carried out in another container and repeating the whole practice several

times to achieve pure kaolin by-product and free of kaolin powder. About 400 gm of kaolin by-product is obtained from

1 kilogram of Kaolin (PKR-13).

2.2 Pre-treatment of Kaolin by Product (Residue)

The residue obtained from kaolin was treated with sulfuric acid to illiminate iron oxide from the material. For the

removal iron oxide 250gm of kaolin by product was washed, dried and mixed with 500 ml of 4M solution of H2SO4 and

the mixture was stirred with magnetic stirrer for whole night at room temperature. After acid treatment material obtained

was rinsed with sufficient quantity of demineralized water and dried at 105 oC for 24 hours in forced convection oven.

The dried material obtained was sieved to 200 microns [12]

213



2.3 Calcination of Kaolin by Product mixture

Weighed amount of SiO2 and Sodium Silicate was mixed. The mixture was than calcined in muffle furnace. In muffle

furnace, the material was allowed to react at a high temperature (850 oC) for two hours, where a chemical reaction

between SiO2 and Na2CO3 took place to produce sodium silicate as shown in chemical equation (1) Then material was

then left in open atmosphere for cooling.

3SiO2+Na2CO3⟹ 3SiO2. Na2O+CO2↑ (1)

The product; sodium silicate was sieved to obtained 100micron particle size for further processing [13]. Through

calcination at high temperature less reactive kaolin residue was converted into more reactive form with the addition of

certain ratio of sodium carbonate.

2.4 Kaolin residue & Sodium carbonate ratio

A varying amount of kaolin residue was calculated and mixed with different amount of sodium carbonate to obtain

mixture with varying ratios of kaolin residue to Na2CO3 (i.e. 1,3). The mixture was put in muffle furnace at 850 oC for

two hours to be calcinized. The material was allowed to remain within furnace until it was cooled to room temperature.

The chemical bonds between Si-O-Si and Si-O-Al were being broken if sodium carbonate was mixed with calcinizing

material, and chemical reactions are given below. If Na2CO3 is mixed and heated. The kaolinite was transformed to

reactive products of NaAlSiO4 and NaSiO3. The chemical reactions of the kaolin and Na2CO3 mixture in

3SiO2+Na2CO3⟹ 3SiO2. Na2O+CO2↑ (1)

The traces of Al4Si4O10 in vitreous material reacts with Na2CO3 as shown in equation (2);

Al2O3 ∙ 2SiO2 ∙ 2H2O + Na2CO3 → 2NaAlSiO4 + 2H2O ↑ +CO2 (2)

Adequate amount of sodium silicate is essential for accomplishing complete reactions as shown in above equation (2),

but superfluous Na2CO3 in mixture remains intact as an impurity so, it is necessary to acknowledge its right amount to

be used [17].

2.5 Neutralization of Vitreous Material

Succeeding to the grounding, the resultant product obtained from the calcination usually called vitreous material a

quantity of (10gm) was allowed to dissolve in 250ml of demin water (50 oC) to form hydrated sodium silicate. The pH

of hydrated sodium silicate solution was measured with pH meter under continuous stirring at room temperature. The

vitreous material obtained after calcination was observed basic in nature and its pH was measured about “pH=12.09” of

sample with molar ratio n=1 and pH for sample with molar ratio n=3 was measured “pH=11.5” [19].Now three samples

were formed from each sample with molar ratio (n=1,3) so as to form sample of specific pH (i.e. pH=2, 6, 8) required

for further study. Total six samples were formed from these two ratios. Each sample were tagged with specific name

and pH. The pH of each sample was firstly measured to know its original pH either it is acidic in nature or basic in

nature. It was seen in all six samples that they were basic in nature and pHs were around 11.00-12.09.

2.6 Aging Time

Succeeding to alkalination next step was aging the sol gel. Sol gel was soaked in water bath with demineralized water

and it was changed after every six hours and this practice was repeated for 24 hours. The main purpose of aging sol gel

to promote the structural network of the gel and making the gel free from left cationic contaminations [21]. After aging

of silica sol, drying was carried out in an oven at 105 oC for 24 hours.

214



3. Result and Discussion

3.1 Characterization of kaolin by-product

The XRD of kaolin by-product was performed in which X-ray patterns shows peak of quartz prevailing 2θ at point 27.

Other peaks observed 2θ at 22, 37, 51,60, which is also characteristics of quartz and these peaks confirm the siliceous

nature of kaolin by-product.

Fig. 1. XRD Graph of Kaolin By-Product

3.2 Characterization of Sol-Gel

Analysing of Sol-Gel through FTIR as shown in Fig. 2., FTIR spectrum of precipitate sol-gel formed at various pH

values 2, 6, and 8. The spectra pattern are alike and shows low peaks at IR band at 4450 cm-1 with reference to hydrogen

bond with silanol group physically held water molecules [22]. Similarly, the IR band observed at 4260 cm-1 is because

of to and fro motion of water molecules.

The bold and broad IR band at 4375 cm-1 with a linked branch at 3900 cm-1 is normally allotted to transverse-optic and

longitudinal varying optic modes such ‘transverse and longitudinal’ of the Si–O–Si unsymmetrical full extent vibrations

[23]. The IR band could be allotted to silanol groups at 950 cm -1. In case of alkali silicate materials Si-O- asymmetric

stretching vibrations is assigned to this band. This band becomes more intensify as pH increases. The availability of OH

group on the SiO2 surface has been undoubtedly confirmed by several research data and analysis [33]. IR bands at points

1050 cm-1, 3370 cm-1, 4050 cm-1 are due to Si–O–Si, O–Si–O, and O–Si–O symmetric stretching vibrations respectively.

10 20 30 40 50 60 70

0

100

200

300

400

500

600

700

800

Kiolin By Product

inte

sity

2 theta

Quartz

Muscovite

215



Fig. 2. FTIR spectra For Sol-Gel preparation at different pH (2, 6, and 8)

As it can be seen in Fig. 3. XRD spectra do not exhibits any vivid peaks from which it can be easily confirmed that sol-

gel obtained is not crystalline, but it is amorphous in nature [18]. XRD patterns exhibits wide bands and low intensity

at 2θ 3010 for pH value 2 and at 2θ 2510 for the sol-gel formed at pH values 6 and 8 as shown in Fig. 3 [9]. formed

amorphous SiO2 by using the sol-gel method, and it was subjected to thermally treated, then determined it using the

Rietveld refinement. In this work, an amorphous peak was centered at 2θ at 270.

Fig. 3. XRD pattern of silica gel samples prepared at pH 2, 6 and 8.

In order to investigate the form and structure of porous the silica gel prepared with sol gel method and the kaolin by

product used for this study have been characterized with element scanning microscope (SEM) which magnifies the

product at different magnifications as shown in Fig. 4. The gel sample exhibits great number of pores which looks like

a sponge. The large particle sized investigated by SEM is 2-3 micro meter on average. They make prominent particular

216



morphology and texture for given material.

Fig. 4. SEM micrographics of filtered and dried SiO2 gel obtained (pH 2) at different optical magnifications, (a) x 5000 and (b) x1000

4. Conclusion

This research was intended to exploit indigenous Thar Parkar Kaolin by-product for the synthesizing of silica gel which

is discovered to be outstanding for the purpose of manufacturing of high-quality glass wares. In addition to this siliceous

by-product of Thar Parkar kaolin found ideal for the formation of sodium silicate which is the precursor in synthesis of

silica gel which in turn is used in preparation of high-quality glass wares. The silica gel is obtained by neutralizing

diluted sodium silicate with 2M HCL solution.

In this work, the structure of the silica gel obtained was determined by different analytical techniques. The results

obtained exhibits that silica gel is amorphous in nature which is suitable for glass ware preparation. The filtered and

powder silica gel obtained at pH 2 reached a specific surface area as high as 470.2 m2/g which is closer to the specific

surface area ‘477.9 m2/g’ of the Algerian siliceous by-product of kaolin studied. These characteristics exhibits a great

adsorption capacity and high porous texture. The X-ray diffraction spectra does not highlight a well-defined crystalline

structure which means obtained product (silica gel) is amorphous in nature.

Acknowledgements

The authors acknowledge the Department of Chemical Engineering, Mehran University of Engineering and Technology,

Jamshoro for providing the research facilities.

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A Revitalization of traffic management Plan and the impacts of Hawker in Saddar bazaar Karachi

Furqan javeda, Sania Rehman Memon b

DUET, Architecture department, Karachi and 75300, Pakistan MUET, Architecture Department, Hyderabad and 71000, Pakistan

Abstract

The urban economy in any society represents primarily the use generating sources the formal organized and also the informal unorganized sector. In most Asian country cities, the urban poor survive by operating within the informal sector. For these urban poor, street vendition is a method of earning a living. However, few hawkers live close to their place of labor and travel long distances by bus or two-wheelers. It is true that hawker’s encroachment reduce the area vacant for walkers and travelers, which creates traffic congestions. Traffic blocking is one main problem that most of public suffer every day in a big city like Karachi. Karachi’s central coach station is additionally set in Saddar, therefore connecting it with different areas of Karachi making an enormous issue as Encroachment in Saddar is outlined because the outlaw occupation or global organization authorized use of belongings and land. Sporadically, anti-encroachment drives by the town government have evicted these hawkers and vendors out of the Bazaar. The proposal present in many alternatives to the traffic plan, Re-routing public transport Remove hawker’s settlement it develop Saddar into a pedestrian zone the concepts behind this proposals type the premise of a future revitalization plan for Saddar and Area cognitive map, then Saddar may often reborn into a multi-class amusement and recreational space that the current day socially fragmented metropolis urgently desires. The data has been collected from the respondent and visitors of Saddar bazaar to gather the main problems through questionnaire survey to observe existing conditions of Saddar habitants Revitalize the original life style of Saddar; making it a shopping and cultural magnet for visitors as well as tourists.

© 2018 Furan jived, Sania Rehman Memon Selection and/or peer-review under responsibility of Energy and Environmental Engineering Research Group

(EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: central bus station, Encroachment, hawker’s settlement

1. Introduction

Many urban areas of Asian cities are environmentally degraded over time because of unplanned transport connected activities

and also the development of hawker areas around them. A number of these areas contain the built-heritage of the cities and were

once centers of culture, amusement and recreation. Saddar is one of such space and which customs greatly of the historical royal

core of the town. Saddar City holds the biggest attention of British colonial architecture in Karachi [1]

Saddar city is that the main business space of city, with the central looking space found within the historic Empress Market

additionally because the Central railway and the Central terminus and therefore the close Port of city [2] Thus it is necessary to

grasp the origin and also the Revitalization of Saddar through Re-routing transport system, habitant hawker’s and Improve Saddar

into a pedestrian zone. [3]

Corresponding author. Tel.03473666814


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Fig.1. Boundaries of Saddar Area in Karachi

2. The problem and its Background

Karachi is that the quickest rising extra-large town with in the world each in proportion and expansion. Its population has enlarged

by over one hundred pc from eleven million (figure of 1998 census) to 22 million once the household amount was shown. As

such, city holds 10% of the population of Pakistan and 22% of its city populance [4]. Karachi is additionally the capital of Sindh

region. It contains 62% of Sindh inner-city populace and 30% of its total populace. Due to movement from Bharat when 1947

and nonstop movement from different components of Pakistan, city could be a multi-ethnic town. [5]

The study area comprises the commercial core of Karachi. Saddar the city center, is the main shopping area of Karachi with

thriving markets.

2.1 Transports system in Saddar Karachi

In spite of Karachi’s importance, its transport connected issues have raised significantly. the quantity of conveyance registered

buses has declined from 22,313 in 2011 to 12,399 in 2014 of that 9,527 are operative because of this failure, folks are enforced

to travel on the roofs of buses that is to be precise extralegal and wait at bus stops for lengthy period to urge a ride. An oversized

variety of buses have born-again from Diesel to CNG as a result of a judicial writ. However, because of deficiency of offer, CNG

sale solely permissible for four days per week and it's only on nowadays that CNG buses will perform. This creates further issues

for the commutation public [6]

Fig.2. Existing and proposed traffic routes at Saddar Karachi

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The significance of the matter may be refereed by the actual fact that in 2011 solely 0.85 % automobiles in metropolis were bus

and 4.04 % were 3-seater motor rickshaws (these square measure three wheeler vehicles), whereas cars deep-seated 81.21 % and

motorcycles deep-seated 49.59 % (for details see, Table -1).

The effect of traffic blocking on the city Decreased mobility, High levels

of nephrotoxic air additionally as sound toxic waste, Environmental degradation and demolition of the

urban landscape, Deteriorating alive values, exaggerated direct and indirect prices being

specifically, prejudicial impact on bus transport as buses area unit stuck in traffic severely moving fleet productivity [7]

Table.1. model distribution of vehicles and passengers and the number of vehicles registered in Karachi in 2013(Source: Transport and

Communication Department, Karachi Municipal Corporation)

2.2 The Hawkers of Saddar Bazaar

In Third World cities, hawkers occupy pavements and in several cases even road area. Their popularity works where poor people

live or work, or in the area where they are transported and traveling. This is often due to the advantages of land or tradesmen of

the city or traders, and there are no plans for their place of sale and the demand for sale. The state government's response to social

problems is to abandon them. It is commonly occurring in Manila, Jakarta, Bombay and Karachi, and the cities of the Third World

[8]

In some cases, governments have wanted to restore hawkers. This rehabilitation has not been complicated, it is not considered a

link between public transport, public transport, buses and hawkers.

In 2001, a serious eviction of hawkers was administered by the authorities within the Saddar space. They were settled from the

most roads to the lanes within the same space. They rejected this relocation and when a three-week amount they managed to bribe

their method back. The URC had opposed the eviction and at a gathering of its board, it absolutely was determined that a practical

set up for hawker’s rehabilitation in Saddar ought to be developed. It absolutely was additional determined that hawkers were a

necessity for the low-income residents of town and conjointly evicting and relocating them would impoverish their families

during an amount of inflation and recession. [9]

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Fig.3. Traffic rushes and hawkers of Saddar

Fig.4. Location of existing hawkers, Encroachers and leased market

3. Model Revitalization Proposal:

Saddar’s issues will solely be solved as a part of a bigger town planning exercise that deals with the traffic and transport

issues of town. Area cognitive map and plan for the revitalization of Saddar have been made as Model Restoration

Proposal. It is tough to contrivance because habitants overlook the realisms that this statement contracts with.

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Fig.5. Mental Mapping of Saddar

Fig.6. Space Recognition Map

As shown in space recognition map hawkers and encroachment occurs in most valuable urban space like empress

market which causes the huge traffic flow problems. 3.1 Alternative Solution

I have mark a substitute plan for this part, I have mark the bazaar area a non-motorized sector and reserve the central

approach street to the place for public transport. As from experience it came to knowledge that pedestrian-friendly streets

are great for business. Second, it provides more opportunities for improved transport services for the more distant areas

served by the Karachi.

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https://thecityfix.com/persuading-for-pedestrian-zones-part-2/


Fig.7. The proposed revitalization map with Pedestrianization rerouting of vehicular movements / Public Transportation

According to the arrange, all the general public transport coming back from MA Jinnah road/ FTC side, presently

terminating at Mansfield Street, Shahrah-I-Iraq, Saddar Dawakhana and encompassing streets, would be taken a turn

from the lucky star chorangi and crossing the Dr daudpoto road and end at MA Jinnah road. Follow up these pattern for

transport routes can less the traffic problems from the town.

4. Conclusion:

Encroachment is the biggest problem in Saddar Town. Which has become a thriving business and the administration

seems to be utterly failed to control the problem. A large number of shopkeepers have put up roadside stalls in complete

violation of laws. Forty to seventy percent width of streets and roads is occupied by vendors, while footpaths are also

mostly occupied by shopkeepers and vendors, allowing very little space on streets and footpaths for vehicular traffic and

pedestrians. The locations where they are Encroaching at present need to be re-plan to accommodate them in a manner

in which they do not adversely affect the existing and proposed transport systems.

5. Recommendations

The authors are grateful to the Almighty Allah, for His kindness. All praises are for Him and all respects are for His

Holly Prophet (PBUH.) who guided us to recognize our Creator. The authors acknowledge the guidance and support

received from teachers and friends. The author would like to thank EESD and Mehran University of Engineering &

Technology, Jamshoro, Pakistan, for providing place and their support in writing this paper.

References [1]. F. Malik , “Heritage Foundation calls for restoration of Calcutta House in Karachi”, The Express Tribune.Karachi,Pakistan (newspaper).

Retrieved 7 April 2018: https://tribune.com.pk/story/1670686/1-heritage-foundation-calls-restoration-calcutta-house-karachi/

[2]. Z .Waseem,”Wandering in wonder: A new way to visit Karachi”, Dawn (newspaper), Published 19 January,2015, Retrieved 7 April ,2018: https://www.dawn.com/news/1158031

[3]. A. Hasan, A. Sadiq, P,Christophe, “THE HAWKERS OF SADDAR BAZAAR A Plan for the Revitalisation of Saddar Bazaar Karachi Through

Traffic Rerouting and the Rehabilitation of its Hawkers”,karachi, Ushba Publishing International,2008: http://arifhasan.org/wp content/uploads/2017/03/SaddarBazaarBook.pdf

[4]. W. Cox, “World Urban Areas Population and Density, New Geography”, 05 March,2012: http://www.demographia.com/db-worldua.pdf

[5]. I. A. Kaimkhani,”Master Plan Group of Offices (MPGO)”, Karachi Strategic Development Plan-2020; CDGK, 2007, https://www.scribd.com/doc/6788059/Karachi-Master-Plan-2020

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https://www.dawn.com/news/1158031

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[6]. M. Raza, “Karachi’s Transport Issues: A diversity of stakeholder perspectives”, Presentation at the Karachi 9 Conference 2016, 22 November, 2016: http://pubs.iied.org/pdfs/10773IIED.pdf

[7]. D. Bertsimas, S.S. Patterson, “The Traffic Flow Management Rerouting Problem in Air traffic flow control: A Dynamic Network Flow Approach”, Published Online:1 Aug,2000: https://pubsonline.informs.org/doi/10.1287/trsc.34.3.239.12300

[8]. A.Hasan, C. Polak, A. Sadiq, “The Hawkers of Saddar Bazaar. Ushba Publishing International”, Karachi 2008: http://arifhasan.org/books/the-hawkers-of-saddar-bazaar

[9]. Muhammed. S, “URC , Urban Public Transport and Sustainable Livelihoods for the Poor”, a Case Study: Karachi, Pakistan, Loughborough University 2000:https://core.ac.uk/download/pdf/2745440.pdf

225

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https://pubsonline.informs.org/action/doSearch?text1=Patterson%2C+Sarah+Stock&field1=Contrib


Developing Silver Nano Particles Based Optical Sensor for H2O2

Detection in Environment

Hima Zafara,*, Sirujddinb, Kausar Rajarb, Bhawani Shankar Chowdharya, Rahat Ali Khanc

a Department of Electronics, Mehran University of Engineering & Technology Pakistan 76080 b National Centre of Excellence in Analytical Chemistry University of Sindh Pakistan 76080

c Institute of Information and Communication Technology University of Sindh Pakistan 76080

Abstract

Hydrogen Peroxide has several applications which make it a very useful chemical. The negative side of this chemical is

that when it combines with other compounds and easily turns into an explosive. Further, it has been found to be used

for mass destruction. This paper is about developing optical sensor to detect its presence. The technique used in this

paper is based on the development of colorimetric sensor using Silver Nano-Particles (AgNPs). Silver nano-particles

have been developed after heating the solution mixture of Silver Nitrate and Polyvinyl Pyrolidone (PVP) as capping

agent at an elevated temperature. Later, the synthesized silver nano particles were optimized via several parameters like

pH, capping agents and stability study. The prepared silver nano particles were characterized via different techniques

such as UV-Visible Spectroscopy and Fourier Transform Infrared (FTIR) spectroscopy. Finally, fabricated AgNP was

used to develop colorimetric sensor with an absorbance of 400 nM for the detection of hydrogen peroxide (H2O2)

concentration in the linear range of 1.6 ×10-6 to 1.6 ×10-4 M. Likewise, the limit of Detection(LOD) and limit of

Quantification (LOQ)is calculated to be 1.4×10^-7 M and 4.66×10^-7 M. This developed sensor opens new perspective

of detecting on-site reactive oxygen species and other types of analytes in future.

© 2018 Hima Zafar, Sirujddin, Kausar Rajar, Bhawani Shankar Chowdhary, Rahat Ali Khan. Selection and/or peer-review under responsibility of

Energy and Environmental Engineering Research Group (EEERG), Mehran University of Engineering and Technology, Jamshoro, Pakistan.

Keywords: Silver Nano particles, UV-Visible spectrometry, Polyvinyl Pyrolidone, Colorimetric sensor, Hydrogen peroxide

1. Introduction

Hydrogen peroxide (H2O2) is very important industrial chemical. This chemical is used in many fields like electronic

industry, textile industry, waste water treatment industry, chemical synthesis industry and so on [1]. H2O2 is commonly

produced on an industrial scale through a process known as the anthraquinone oxidation process. This process causes

environmental pollution [2], [3].

We have witnessed that several incidents have occurred which have used hydrogen peroxide as an explosive agent. This

chemical could become an explosive because this is an oxidizer and if it reacts with other components it becomes

explosive [4].

This was the motivation for the proposed work that this chemical can easily be detected through the proposed synthesized

sensor. Nanotechnology is the hottest field of investigation and innovation in current scenario. Materials ranging from

1–100 nm are considered to fulfill the definition of nanomaterials. The area of nanotechnology has proved to get

marvelous growth and innovative advances across electronics, medicine, robotics, communication, chemistry and

physics [1, 2]. The metal nanoparticles, especially AgNPs are of special focus to scientists due to their Localized Surface

* Corresponding author. Hima Zafar


226



Plasmon Resonance (LSPR) properties, which later define its composition, size, shape, refractive index and surrounding

texture [7]. LSPR produces strong spectra of resonance absorbance peak shift in the visible band of light with a smallest

change in refractive index of the medium [4, 5]. AgNPs are the most commercialized nano-material based products per

year [8]. Generally metal nanoparticles can be synthesized by chemical reduction [5], green [9] and microbial methods

[10]. Among them chemical reduction technique is proved to be the best for the fabrication of nanoparticles with varied

sizes and shapes , nano rods, nano wires, nano prisms and nano plates [11]. The steps required for the development of

AgNPs are (i) Reduction of Silver Nitrate using reducing agent like glucose, sodium borohydride, tri-citrate, etc. [12]

(ii) Prevention of AgNPs from agglomerating. Stabilizing agents play very important role as they protect NPs to bind,

absorb or lose their surface properties. Polymeric compounds like Poly Vinyl pyrrolidine have proved to be excellent

defensive agents, are also as used in this experiment.

The development of highly sensitive and selective analytical tool for the detection of hydrogen peroxide (H2O2) is used

in this process. Similarly, Hydrogen peroxide is strong oxidizer n reducer depending on pH, it is more viscous than

water and used with fuel in Rockets. Low concentration of H2O2 which is 6%, is only being used for medication,

treatment of water, etc., as per Material Safety Data Sheet (MSDS) if higher concentration of H2O2 is used than it acts

as aggressive oxidizer and can be explosive once it encounters any organic compound in surrounding. The nanozyme-

based detecting stages offer promising new ways in H2O2 discovery, however with a specific end goal to acquire and

keep up the high synergist action of the nanozymes, strict control of the examinations and union conditions are ordinary

required [13],[14], [15].

One of the scholar, Tagad et al. [16] from India has used green synthesis method using Locust Beam Gum (LBG) to

detect H2O2 using a U bent sensing probe fabricated by Polymer optical fiber, which is new mechanism towards

engineering, but it’s typical to develop. Another scholar Wenbig et al. [17] from china demonstrated intrinsic activity of

Carbon nano-dots in the catalysis of 3,3’,5,5’ Tetramethylbenzidine (TMB) or is also known as visualizing regent used

in staining procedure in immunochemistry for the detection of Hydrogen peroxide and glucose in serum.

Qi Rui et al.[18] from china used electrochemical approach to develop third generation biosensor based on direct electron

transfer (DET) with modified metalloprotein cytochrome c (cyt.c) achieved at ZnO nano sheet using one step deposition

for the cathodic detection of H2O2 by avoiding O2 interferences and anodic interference like Ascorbic

Acid(A.A),dopamine(DA) at the same time. This biosensor used to determine H2O2 released form living human

hepatoma cells. Another scholar Miao et al.[19] from United states proposed sensory material ,based on cellulose

microfibril coated with Ti(IV) oxo complex for the vapor detection of H2O2 in peroxide explosive such as triacetone

triperoxide (TATP) using paper-based colorimetric sensing system.

There is a need of such sensors and transducers that are hand-carrying and provide efficient, reliable, sensitive and give

accurate results. The sensors can differ according to different nanoparticles core material (whether its metal, polymer,

oxides or composites) size, shape, surface chemistry, and their physical properties (such as electrical, optical, magnetic,

chemical, etc.). Therefore, optical Plasmon and absorption properties of metal nanoparticles has been useful in

colorimetric sensor for detecting various harmful chemicals in an aquatic environment [20].Indeed , solution to this

colorimetric method for sensing, owing the simplicity and cheapness have attracted many to conduct research [21]

.Colorimetric approach Silver nanoparticles shows excellent , easy visualization of colour change between individual

nanoparticles and aggregated ones ; yellow to colourless in real-time [22].

In this paper we have worked on the development of silver nanoparticles which are through chemical reduction method.

The reducing agent in that process was NaBH4 and PVP as capping agent which is polymeric surfactant and saves the

metal nanoparticles from aggregation; to detect Hydrogen peroxide (H2O2) which is found to be an easy method to

construct this, for the first time in the locality of Hyderabad -Pakistan. This method is simple to construct, speedy to

process and economical.

2. Material and Methods

2.1 Reagents and Chemicals

AgNO3 (Silver Nitrate), PVP, NaBH4, NaOH (98%), HCL (37%), NiCl2, Ascorbic Acid (C6H8O6), CoCl2.6H2O, Pb

(NO3)2, ZnCl2, KOH, NaCl2, CuSO4.5H2O, HgSO4. H2O, H2O2 were obtained from Sigma-Aldrich. All stocks solution

was prepared from Mili-Q water.

2.2 Characterization Method

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The prepared Ag nanoparticles were characterized by Ultra violet spectroscopy (UV/Visible) in aqueous form using

Perkin-Elmer 365 instrument on initial stages for the confirmation of the formation of AgNPs through reported peaks.

While to see the functional groups attached, Fourier Transform Infrared Spectroscopy analysis (FTIR) dry powder of

AgNPs was obtained and tested using Thermos Scientific Nicolet TM iS10 (with a range of wavenumber 400- 4000 cm-

1 ) under ATR mode. For 2D image of particles Scanning Electron Microscopy Model: JEOL: JSM-6380Lwas used.

Note: Except U-Visible spectroscopy all other methods used the particles which were dried in petri dish, washed by

acetone and then kept in oven (80 °C) for 10minutes to get impurities free silver nanoparticles in dry-powder form for

further characterization method. The visualizations of the colorimetric essay are discussed further.

2.3 Procedure for synthesis for silver Nano particles

First, we took 0.0001 M of NaBH4 in 10 mL Milli-Q water, kept on stirring for 15 min, by adding 20 µL PVP of 0.7%

M, and then 10 µL of AgNO3 of 0.1 M concentration drop by drop. The transparent solution is gradually converted into

bright crystal yellow color indicating the formation of AgNPs. Once the reaction is completed it is no longer needed to

be kept on stirring plate. This synthesis was realized at room temperature with pH value of 6.0.

3. Results and Discussion

3.1 UV-Visible Analysis

AgNPs show surface plasmonic resonance in UV-Visible spectra, hence UV-Vis spectroscopy was used as key technique

regarding initial characterization of PVP derived Ag-NPs which was centered between 350-470 or 500 nm depending

on the size. The AgNPs were synthesized in aqueous medium using NaBH4 as reducing and PVP as capping agent.

Different optimization parameters of reaction were observed such as: 1) optimization of NaBH4, selecting 0.001 M

concentration in 10 mL water with; 2) PVP of 20 µL along with stirring for 2 min and finally adding 3) 10 µL of AgNO3

of 0.1 M concentration. Once pale-yellow color was developed, it was taken for U.V-Vis test, optimizing some in-vivo

effects like pH, heating and found that 1) there was no pH effect and its original pH 6.0 was selected. 2) Room

temperature found to be suitable for the particles. The perfect absorbance recorded for this Ag NPs is 400 nm as in Fig

1.

Fig 1: UV-Visible spectra of PVP coated AgNPs

3.2 Fourier Transform Infrared (FTIR) spectroscopy Analysis

Each repeating unit of PVP has two functional groups, a C–N group and a C=O group. These groups, due to their N and

O atoms, have great affinity for silver ions and can coordinate metallic silver. PVP-coated AgNPs yielded man strong

absorption of C–N peak of pure PVP at 1017 cm-1 which is separated into two peaks at 1070, and 1000 cm-1. Furthermore,

the peaks at 1408 cm-1, 1603 cm-1, 3333 cm-1 are characteristics of bond vibrations of the NO3-1 group, C-O bonds, and

228


O–H stretching bands in Figure 2. Therefore, the spectrum of FTIR show cases the molecular connections between

AgNPs and PVP series.

Fig 2: FTIR spectrum (a) PVP standard (b) PVP coated AgNPs

3.3 Scanning Electron Microscope Analysis (SEM)

A Scanning Electron Microscope (SEM) is a type of electron microscope that produces images of a sample by scanning

the surface with a focused beam of electrons. This technique is useful to visualize the shape of your nanoparticles in 2D

form. Fig 3 illustrates the scanning electron microscopy (SEM) images of AgNPs nanoparticles in 5 µm to 2 µm. It can

be seen clearly in the SEM images of the PVP synthesized AgNPs are well-defined petals-like particles.

(a) (b)

Fig 3: (a) scanning electron microscopy morphology images (a) 5 µm (b) 2 µm

3.4 Detection of H2O2 using synthesized AgNPs

The colorimetric sensing of hydrogen peroxide was performed by taking 10 mL test tube, with 2.5 mL of synthesized

Ag nanoparticles and different concentrations including 70%, 50%, 30% & 10% of H2O2 was added one by one by

following the most recent reported experiment [23] until the solution turned transparent . After optimization we selected

30% of H2O2 for further work. The assay of H2O2 was transferred to quartz cell to investigate the optical changes within

5-minute time on UV-V as shown in Fig 4 (a) to implement potential colorimetric sensing application.

The method exhibited well linearity in the calibration range 1.6 ×10-6 to 1.6 ×10-4 shown in Fig 4 (b). The correlation of

determination (R2) was 0.99, with Limit of Detection (LOD) and Limit of Quantification (LOQ) calculated to be 1.4×10-

7 and 4.66×10-7 M correspondingly.

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(a)

(b)

Fig 4 (a) Decrease in absorbance with decreasing concentration of (b) linear Regression plot between absorbance and hydrogen peroxide

concentrations.

3.5 Selectivity of sensor

To check the selectivity of PVP-coated AgNPs for other heavy metal ions and biologically important analytes, we

observed that the colorimetric results in the presence of various metal ions including Ni2+, A.A, Co2+, Pb2+, Zn2+, K+,

Na+, Cu2+, Hg2+, H2O2 at concentration of 100 micromolar. The selectivity of developed sensor can be checked visually

as reported by the inset photograph in Fig 5 (a) and (b).

200 300 400 500 600 700 800

0.0

0.5

1.0

1.5Absorbance

Wavelength

y = 0.0619x + 0.2501R² = 0.9908

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 2 4 6 8 10 12 14 16

Chart Title

Ab

sorb

ance

230


(a)

(b)

Fig 5 (a) Photograph of heavy metal ions (b) UV-Visible spectrum of Metal ion

3.6 Results

A comparison of the limit of detection for hydrogen peroxide obtained by the present method and existing four methods

is dicussed in this section. Limit of Detection (LOD) should be low as it tells that up to what minor value a sensor can

detect the targetted analyte. Linear Range is the range of spiking the H2O2 in medium that should also be low. This helps

in proofing that a sensor can detect the minimum presence of this dangerous analyte. Linear Range is supporting value

for LOD. As it can be observed that work proposed in [15] used Graphene-Oxide Modified with AgNPs method, [24]

used Tri-Sodium Citrate capped AgNps using Lee-Meisel Method, [25] used Silver Chloride Nano particles Using

Sargassum algae method and the proposed work has used PVP-coated AgNPs method. In proposed work and other

existing works [15], [24] and [25] the medium in which H2O2 was tested is water. In [15] the LOD is 2.0 × 10−8 M, in

[24] the value of LOD is 2.0 × 10−8 M, in [25] the value of LOD is 9× 10−8 M and the proposed work has achieved LOD

value of 0.14× 10−8 M. This shows that the proposed work has least value of LOD as compared to other existing works

with good sensitivity.

In [15] the Linear Range is 5 × 10−6 to 8 × 10−5 M, in [24] the value of LOD is 2.5 × 10−6 to 4 × 10−5 M, in [25] the value

of LOD is 1× 10−6 to 1.1 × 10−4 M and the proposed work has achieved LOD value 1.6 ×10-6 to 1.6×10-4 M. Here [25]

has least value of Linear Range. As discussed earlier that Linear Range supports LOD which means that the proposed

work is better than others because it has the least value of LOD.

4. Conclusion

In summary, we first synthesized the AgNPS using different reagents and found PVP as capping agent suitable for our

work, which showed the stability of five months. Later PVP-coated AgNPs were characterized by UV−visible, SEM

analysis and FT-IR spectroscopy. Moreover, developed fabricated optical sensor, is a simple and rapid and highly stable.

Colori-metric assay was used for quantitative detection of Hydrogen Peroxide (H2O2). H2O2 which is strong oxidizer,

also used widely in food industry, but at the same time is very dangerous if encounters any organic compound in

surrounding. To avoid the usage of this harmful analyte in our locality Hyderabad-Pakistan we developed a simple

AgNPs Ni2+ A.A Co2+ Pb2+ Zn2+ K+ Na+ Cu2+ Hg2+ H2O2

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colorimetric sensor for the detection of H2O2 in medium like water; as tested initially. This method is very sensitive

linear range with limit of detection and quantification found to be 1.4×10-7 and 4.6×10-7 M respectively. Hence this

detection method has potential application in environmental monitoring handy kit plus it can be extended for the

development of membrane for the water purification.

Acknowledgement

We are thankful to Roomia Memon, Gulnaz Laghari who helped in the research and National Centre of Excellence in

Analytical Chemistry University of Sindh Pakistan for allowing to use their resources.

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