1 Influence of Periwinkle shell ash inclusion on temperature – dependent electrical properties of cement paste

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9 Abstract
10 This study sought to examine the influence of Periwinkle shell ash (PSA) inclusion on electrical properties of
11 cement paste. Shells of Periwinkle collected as waste materials were processed into the ash. Pastes were then
12 prepared using Portland cement only (PCP), mixture containing 10 % PSA and 90 % cement (CPSA), and the ahs
13 only (PSAP). The pastes were cured with the same volume of water for 14 days and under same climatic
14 conditions. The results of experiments conducted on them showed that they exhibited negative temperature
15 coefficient of resistance with PCP recording -10.7 while CPSA and PSAP recorded -11.6 and -10.9 (all in %/K)
16 respectively. Electrical resistivity of PCP, CPSA, and PSAP was found to be 9.62 x 102 Ωm, 2.31 x 102 Ωm, and
17 8.99 x 102 Ωm respectively. More so, thermal sensitivity index of 7978 K was obtained for PCP, 8667 K for
18 CPSA, and 8143 K for PSAP. Findings from the study showed that although all the pastes have sensing ability,
19 inclusion of PSA in cement matrix could enhance improved sensing ability. Since paste is popularly used for
20 plastering purpose, the practice of using composite paste made from cement and PSA could ensure large sensing
21 volume for temperature changes of building structures. In addition, utilizing Periwinkle shells as described herein
22 would help to mitigate the adverse effects caused by improper disposal of the shells.
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24 Keywords: Building structure, Electrical resistivity, Temperature monitoring, Thermal sensitivity index, Waste
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26 1.0 Introduction
27 Housing development is an important undertaking that aims at ensuring availability of shelter as a basic need of
28 humans. For such to also be affordable, it has become pertinent to address high (and incessant rise in the) cost of
29 building materials. Cement is one typical building material affected in this consideration and it is a basic
30 requirement for preparation of any masonry unit used in buildings. By using 5 t0 10 % of sawdust ash as a partial
31 substitute for cement, concrete with desired strength can be prepared [1]. Improvement in compressive strength
32 of concrete is also feasible with rice husk ash inclusion as partial replacement of cement [2, 3]. Ganesan et al [4]
33 found in their studies that effective improvement in compressive strength, splitting tensile strength, and resistance
34 to corrosion penetration could be achieved for hardened concrete prepared with 20 % of bagasse ash as admixture.
35 More so, Charitha et al [5] reported on the possibility of blending concrete with sugarcane bagasse ahs, wood ash
36 or palm oil fuel ash for drying shrinkage reduction as well as similar utilization of wheat straw ash or bamboo leaf
37 ash for reduction in sorptivity.
38 Application of electrical behaviours of cement-based systems to monitor and predict their performance in service
39 has gained growing attention in recent years. This, plausibly, is because it can help to avoid costly repairs by early
40 diagnosis and treatment of potential durability problems. It is well established in previous studies [6 – 8] that
41 electrical characteristics of cement-based materials have close relationship with other properties such as durability,
42 permeability, freezing resistance and so, they remain vial parameters when studying and evaluating them.
43 Interestingly, Rajabipour and Weiss [9] reported that internal humidity of concrete can be estimated directly based
44 on its electrical conductivity. Chung [10] carried out a research on the resistive , piezoresistive, thermoelectric,
45 and electromagnetic behaviour of cement-matrix composites modified by the use of admixtures like short carbon
46 fibers and short steel fibers. It was observed that short carbon fibers are effective in enhancing the piezoresistive
47 behaviour as well as p-type seebeck effect. On the contrary, short steel fibers were found to be effective for
48 enhancing n-type seebeck effect while submicron diameter carbon filaments effectively enhanced the
49 electromagnetic reflection behaviour.
50 Notably, various grades of materials have been used to construct buildings [11]. Cement has several uses of which
51 one is surface coating of walls in buildings during finishing processes. Also, exposure of buildings to varying
52 temperatures is inevitable. Therefore, it is valuable to monitor temperature of building structures since it affects

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53 their performance, operation, and safety. It is obvious that development of structural and material health
54 monitoring systems could serve as a means to provide life-long quality evaluation and condition assessment of
55 cement-based composite paste. This research is designed to assess the influence of periwinkle shell ash inclusion
56 on temperature – dependent electrical properties of cement paste. As per author’s information, this paper will be
57 the first to report on the use of periwinkle shell ash as proposed. Observably, periwinkle shell is usually discarded
58 as waste and it is majorly under-utilized. In developing countries, solid wastes management systems are
59 inefficient, unsustainable, and devoid of environmental friendliness [12]. Consequently, the prevalent technique
60 of periwinkle shells disposal are indiscriminate dumping and unplanned landfilling both of which constitute severe
61 environmental problems. Hence, there is an urgent need to consider a safe way of valorizing the waste for
62 beneficial purpose(s).
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64 2.0 Experimental part
65 2.1 Materials acquisition and description
66 Periwinkle shells, Portland Limestone Cement (CEM II – BL 32.5R), and potable water were utilized as the major
67 materials in this work. The shells of periwinkle were got from different sources including markets, restaurants,
68 dumpsites, etc while the water was obtained from a borehole. These materials were sourced within Uyo Local
69 Government Area, Akwa Ibom State, Nigeria.
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71 2.2 Preparation of Periwinkle shell ash
72 The shells, as collected (Figure 1), were immersed in water in a plastic bucket for 24 hours. On removal, they
73 were washed thoroughly with water to remove any dirts from them and ensure they were clean enough for use.
74 After that, they were allowed to dry completely in air before being ashed in a Muffle furnace at temperature of
75 950oC. On cooling, the ash material obtained was pulverized using Agate mortar and pestle before it was ball-
76 milled by means of high-energy ball milling machine (Emax, manufactured by RETSCH GmbH). This machine
77 was operated at 500 rpm for 4 hours. It has the capacity to reduce material feed from about 5mm particle size to
78 as fine as less than 80 nm.
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80

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82 Fig.1 Periwinkle shells used in the present study (after washing)
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84 2.3 Analysis of the materials
85 The cement and periwinkle shell ash were analyzed, separately, for chemical composition using X-ray
86 fluorescence analyzer (Spectro X-lab 2000). Also, their loose bulk density was determined by measuring the mass

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 87 of a known volume of each of them and then taking the ratio of the two quantities. Mass measurement was done
88 with the aid of a digital balance (S. METTLER -600g/0.1g) and the loose bulk density was computed as
𝑀
89 𝐷=
𝑉
1
90 where 𝐷 = loose bulk density, 𝑀 = measured mass, and 𝑉 = loose volume of the material.
91 Again, angle of repose was determined by fixed funnel method employing inverse tangent rule [13]. In this
92 research, a plastic funnel was used. While the conical shape of the material heap was forming, the height and
93 radius (half of diameter) of the heap were measured. Five pairs of such parameters were obtained and then used
94 to make a plot of height against radius. The slope of the graph was determined from which the required angle of
95 repose, ∅ was deduced thus
96 ∅ = tan−1 (𝑆) 2
97 where 𝑆 =slope of the graph.
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99 2.4 Samples preparation
100 Three categories of paste samples were prepared, namely, plain cement paste (PCP), periwinkle shell ash paste
101 (PSAP), and cement – Periwinkle shell ash paste (CPSA). Table 1 shows the mix design adopted in this work. In
102 the CPSA, 10 % of periwinkle shell ash included as a partial replacement of cement. This choice was based on
103 several literature reports including that of Lolapo and Umoh [14] supporting it as optimum content for maximum
104 strength in masonry applications. Batching of the materials was by volume method and after being thoroughly
105 mixed with water, each mixture was cast in separate Plexiglas molds of cross-section 52 mm x 25 mm and height
106 14 mm.
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108 Table 1: Mix design used in this study
109 Sample constituent(s) Sample code Number of Water – cement
samples ratio

Cement PCP 5
Periwinkle shell ash PSAP 5 0.5 (constant)
Cement and periwimkle shell ash CPSA 5
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111 Immediately after casting, two copper plates (each with a width of 12 mm and a height of 35 mm) were embedded
112 into the mixture at embedment length and plates separation of 13 mm and 28 mm respectively. These copper
113 plates served as electrodes and they were at same distances from the ends of the samples. All the samples were
114 demolded after 24 hours and then subjected to curing by sprinkling equal volumes of water on them twice daily
115 in a shade. The curing was allowed for 12 days after which they were tested for the intended properties. The age
116 of curing considered in this case was based on minimum of 10 days stipulated for the cement type utilized [15].
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118 2.5 Tests setup and Properties determination
119 The setup used for the tests in this study is schematically shown in figure 2. Since the heating element of the
120 hotplate was larger than the sample, the use of cylindrical aluminium block (of height 80 mm and diameter 75mm)
121 and heat insulant (of very low thermal conductivity measuring 65mm x 65 mm) was necessary to ensure that heat
122 flowed upwardly through the sample (not by absorption of from its sides). The heat insulant used was provided
123 with a central and circular hole for passage of heat from the aluminium block. Separate but identical blocks, digital
124 thermometers (Model 305 quipped with type-K probe), and heat insulants were used for different test schedules.
125 Prior to the test, the sample and its electrodes were thickly lagged using cotton wool.
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132 Thermometer probe

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To LCR meter
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142 Fig. 2 Features of the test setup

143 After the electrode had been connected to the LCR meter (Model No. 9183) for resistance measurement, the
144 control dial on the hotplate was adjusted to a level reasonable enough to ensure a steady flow from the heating
145 element. Temperature monitoring and measurement were actualized with the aid of the thermometer and care was
146 taken to ensure that its probe was in firm contact with the sample’s surface as illustrated in the diagram. Readings
147 were taken at 10oC intervals from 20oC after which the mean and corresponding standard error values were
148 computed for each category of paste samples considered in this research.
149 The electrical resistivity of each sample was determined using the formula [16, 17]
𝜌𝐿
150 𝑅=
𝐴
3
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152 where 𝑅 = mean electrical resistance, 𝐴 = area of the sample’s surface in contact with the electrodes, 𝐿 = electrode
153 separation.
154 From the plot of 𝑙𝑛𝑅 against the inverse of absolute value of temperature, 𝑇 the value of thermal sensitivity index,
155 𝛽 of each sample was deduced based on the relation [18, 19]
𝛽
156 𝑅 = 𝑅𝑜 𝑒𝑥𝑝 [ ]
𝑇
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158 where 𝑅𝑜 = electrical resistance at infinite temperature.
159 Using the thermal sensitivity index obtained in each case, the temperature coefficient of resistance, 𝛼 was
160 determined as [17]
𝛽
161 𝛼 = ± ( 2) 100%
𝑇
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162 (The negative sign is considered only if 𝑅 and 𝑇 relate inversely).
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164 3.0 Results and Discussion
165 Table 2 shows the loose bulk density and static angle of repose of the cement and Periwinkle shell ash (PSA) used
166 in this research. The values of both parameters are greater for the cement compared to the PSA. In the case of
167 loose bulk density, it can be deduced that the cement is 34.81 % lighter than PSA. Based on the flowability
168 interpretations using angles of repose [20], the value for cement (39.5o) and that of PSA (33.7o) indicate fair and
169 good properties respectively. Hence, they may be regarded as being suitable for use as in this case.
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174 Table 2: Particulars of the cement and periwinkle shell ash
Parameters Value obtained per material
Cement Periwinkle shell ash
Loose bulk density (kgm-3) 1254.0 930.2
Angle of repose (o) 39.5 33.7

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176 In Table 3, proportions of chemical oxides in the cement and PSA are presented. All the values fall within their
177 respective ranges stipulated [21] for cement. Not only that, the fractions of SiO2, Al2O3, and Fe2O3 in the PSA add
178 up to 59.23 %, thus showing that it meets the requirements for a class C pozzolan. However, the proportions of
179 CaO, K2O, and SO3 are greater in the cement than in the case of PSA. Contrarily, more of Al 2O3, SiO2, and Fe2O3
180 are present in the PSA than in the cement. By implication, PSA would impart more strength than the cement if
181 used in preparation of masonry materials such as paste and mortar. A greater loss on ignition obtained for PSA
182 (5.79 %) indicates that it contains more carbon-based component than the cement. Other studies have revealed
183 loss on ignition of 7.08 [22] and 4.30 [23] for PSA. The observed variability may be attributed to non-uniformity
184 in calcinations temperature adopted.
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186 Table 3: Chemical composition of the cement and periwinkle shell ash
Name oxide Chemical formula Percentage (wt %)
Cement Periwinkle shell ash
Silica SiO2 17.84 42.34
Alumina Al2O3 3.30 11.64
Ferric oxide Fe2O3 2.56 5.13
Potassium oxide K2O 0.29 0.13
Lime CaO 60.80 29.58
Sulphur trioxide SO3 2.54 0.34
Loss on ignition LOI 1.43 5.81
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188 Table 4 shows the electrical resistance values of each paste sample at various temperatures. PCP has the greatest
189 mean value (172.6 kΩ) followed by CPSA (161.5 kΩ) and then the PSAP (41.5 kΩ). Greater values of electrical
190 resistance obtained for CPSA in comparison with those for PSAP may be due to the fact that it was prepared using
191 a greater fraction (90 %) of the cement. As temperature rises in steps of 10 oC, the electrical resistance of PCP
192 changes by 40.27 %, 36.08 %, 64.64 %, and 74.68 %. Similarly, the changes in the case of PSAP are 59.76 %,
193 72.62 %, 36.96 %, and 58.62 % while the values for CPSA change by 41.92 %, 35.61 %, 65.73 %, and 75.36 %.
194 These portray the fact that marginal changes in the electrical resistance due to temperature rise by a constant
195 amount may not be uniform.

196 Table 4: Electrical resistance of the samples at various temperatures

Temperature, Electrical resistance, 𝑅 (kΩ) of each sample category
𝑇 (oC) PCP PSAP CPSA
20.0 172.6 ± 0.2 41.5 ± 0.3 161.5 ± 0.2
30.0 103.1 ± 0.3 16.8 ± 0.3 93.8 ± 0.3
40.0 65.9 ± 0.1 4.6 ± 0.2 60.4 ± 0.2
50.0 23.3 ± 0.2 2.9 ± 0.3 20.7 ± 0.2
60.0 5.9 ± 0.1 1.2 ± 0.2 5.1 ± 0.3
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198 As evident in figure 3, the electrical resistance of each paste exhibits a non-linear inverse relationship with
199 temperature. Thus, it could be submitted that the studied pastes have negative temperature coefficient of
200 resistance. The nature of it is typifies that of an NTC thermistor. The dependence of electrical resistance on
201 temperature may be attributed to the number of collisions that occur between the charge carriers and atoms in the
202 material. In the instant case, increasing temperature of each paste leads to release of charge carriers further and
203 consequently, the resistance of the paste decreases.

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160 PCP
Electrical resistance, R (103 Ω) PSAP
140 CPSA

120

100

80

60

40

20

20 30 40 50 60
o
Temperature, T ( C)
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205 Fig. 3. Dependence of electrical resistance on temperature of each paste
206
207 The values of electrical resistivity, temperature coefficient of resistance, and thermal sensitivity index obtained
208 for each paste in this work (as presented in Table 5) give substantial support to the fact that inclusion of PSA
209 could improve response of cement paste to changes in temperature. In this study, PSAP contains PSA only whereas
210 PCP contains cement only. Also, for each of the parameters, PSAP has the smallest values among the pastes
211 examined. This, plausibly, is why CPSA has a lower electrical resistivity (8.99 x 10 2 Ωm) compared to PCP (9.62
212 x 102 Ωm). Wen and Chung [24], in their study, observed that addition of carbon fibres (0.5 % of 5 mm size by
213 weight of cement) decreased electrical resistivity of cement paste in the presence of silica fume. In terms of
214 thermal sensitivity, the index values show that the presence of PSA makes CPSA better than PCP. An electrical
215 resistivity value of (9.64 ± 0.08) 10 2 Ωm at 20 oC was reported for a cement paste containing carbon fibres and
216 latex. This compares well with the value obtained for PCP, perhaps, due to the fact that the cement type utilized
217 in this research contains limestone as an admixture.
218
219 Table 5: Computed values of electrical properties of the samples
Sample code Computed values for each sample
𝜌 (102 𝛺𝑚) at 20oC 𝛼 (% /𝐾) 𝛽 (𝐾)
PCP 9.62 -10.7 7978
PSAP 2.31 -11.6 8667
CPSA 8.99 -10.9 8143
220
221 The thermal sensitivity indices (deduced from the plots in figure 4) show rankings having PSAP followed by
222 CPSA and then PCP. As observed, the index increases as proportion of PSA increases, thus indicating that its
223 inclusion improves response of the resulting paste to temperature changes. Indeed, the temperature coefficient of
224 resistance phenomenon itself could be used for temperature monitoring [17]. Conventionally, embedded/attached
225 sensors are usually employed for such purpose in buildings. Unfortunately, those devices are expensive and their
226 sensing ability is location-specific. Interestingly, the cement used in this study can be applied for plastering
227 purpose in buildings. Therefore, with inclusion of the PSA, the self-sensing ability of the paste could be enhanced
228 for temperature monitoring in buildings. In turn, this can help to ensure that advantages such as cost effectiveness,
229 high durability, and large sensing volume are enjoyed as the smart structure responds to temperature changes

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 ln R

12
PCP
PSAP
CPSA 11

10
1/T (K-1)

0.0030 0.0031 0.0032 0.0033 0.0034

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230
231 Fig. 3. Plots of ln R against inverse of absolute temperature
232
233 Conclusion
234 The experimental investigations conducted in this research revealed that Periwinkle shell ash (PSA) and Portland
235 Limestone Cement could be used separately and in combination to develop paste. It was found that the PSA could
236 be regarded as a Class C pozzolan based on its proportions of major oxides such as SiO2 (42.30 %), Al2O3 (11.82
237 %), and Fe2O3 (5.11 %). The electrical resistance, hence, resistivity value of the plain cement paste (PCP) was the
238 highest, followed by that of paste prepared with 90 % cement and 10 % PSA contents (CPSA), and then the one
239 obtained for plain PSA paste (PSAP). The reverse ranking was observed in the case of thermal sensitivity index
240 as the PSAP recorded the greatest value whereas the least value was obtained for the PCP. Though all the pastes
241 exhibited negative temperature coefficient of resistance, the response of PSAP to temperature changes was noticed
242 to be the fastest. The CPSA also exhibited improved response tendency to temperature change, thus signifying
243 that inclusion of PSA could enhance the response ability. Since cement paste is widely used to plaster walls,
244 incorporation of PSA into pure cement matrix could help to ensure large sensing volume as far as temperature
245 monitoring of structures is concerned. This undertaking would also serve as a way of solving waste disposal
246 problems associated with Periwinkle shells.
247
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