Morphology and Thermal studies of Copper Carbonate Nanoparticles * Dr.R.Hepzi Pramila Devamani 1 V.V.Vanniaperumal College for Women, Virudhunagar, Tamil Nadu, India. M.Shameena Begum 2 & R.Suganthi 3 V.V.Vanniaperumal College for Women, Virudhunagar, Tamil Nadu, India. Abstract Copper carbonate nanoparticles were synthesized via chemical co-precipitation method from copper sulphate and sodium carbonate. The formed nanoparticle is characterized by transmission electron microscopy, differential scanning calorimetry technique, thermo gravimetric analysis and differential thermal analysis. The TEM image shows the synthesized copper carbonate show well crystallized particles with spherical morphology. From the TEM image average nanoparticle size, standard deviation and polydispersity can be calculated. The d spacing can be calculated from SAED pattern. From DSC measurements the quantitative and qualitative information about physical and chemical changes that include endothermic/exothermic processes or changes in heat capacity can be studied.. From TGA curve, the decomposition due to mass loss is observed. Keywords: TEM, DSC, TGA-DTA. 1. INTRODUCTION: A burst of research activity is witnessed in recent years in the area of synthesis and fabrication of different size and shape of metal nanoparticles. Amongst many metals like Au, Ag, Pd, Pt, towards which research is directed, copper and copper based compounds are the most important materials. The metallic Cu plays a significant role in modern electronics circuits due to its excellent electrical conductivity and low cost nanoparticles. So Cu will gain increasing importance as is expected to be an essential component in the future nano devices due to its excellent conductivity as well as good biocompatibility and its surface enhanced Raman scattering (SERS) activity [1]. In this work, copper carbonate nanoparticles was prepared and their morphological and thermal properties were studied. Copper carbonate is used as pigments to impart color to paints and varnish, in pyrotechnics, such as fireworks, and in pottery glazes, in animal feeds and fertilizers, in the manufacture of fungicides, in the preparation of alkaline copper quaternary ammonia compounds for treated lumber. 2. MATERIALS AND METHODS: Nanoparticles of copper carbonate were prepared by chemical co-precipitation method by adding copper sulphate and sodium carbonate. Precise amounts of reagents taking into account their purity were weighed and dissolved separately in distilled water into 0.1M concentration. After obtaining a homogeneous solution, the reagents were mixed using magnetic stirring. The precipitate was separated from the reaction mixture and washed several times with distilled water and ethanol. The wet precipitate was dried and thoroughly ground using agate mortar to obtain the samples in the form of fine powder. 3. RESULTS AND DISCUSSION: 3.1. TEM ANALYSIS: Fig.1 shows the TEM images of the synthesized copper carbonate nanoparticles. The TEM images show the spherical morphology of copper carbonate nanoparticles. The size distribution histogram of fig.1g is shown in fig.2. TEM images show that copper carbonate nanoparticles are having particle size 5.7nm. The size distribution histogram for copper carbonate nanoparticles shows 1
the average particle size is 5.7±4.9nm. The standard deviation is 5nm and the polydispersity of calcium carbonate nanoparticles is 87%. Fig.1 TEM images of copper carbonate nanoparticles _B 40 30 Frequency 20 10 Data: Graph1_Counts1 Model: Gauss 0 0 10 20 30 40 50 Diameter(nm) Chi^2 = 4.18234 R^2 = 0.98744 y0 0 ±0 xc 5.65553 ±0.31863 w 9.92228 ±0.75258 A 536.95458 ±31.86769 Fig.2: The size distribution histogram for copper carbonate nanoparticles The SAED pattern of copper carbonate nanoparticles is shown in fig.3. It shows the particles are crystallized. By indexing the SAED pattern the d spacing of copper carbonate nanoparticles is found to be 3.5905 nm and 1.2574nm which matches with the data in JCPDS file 70-2053which shows the diffraction rings on SAED pattern matches with the XRD pattern [2]. 2
Fig.3: The SAED pattern of copper carbonate nanoparticles 3.2. DSC ANALYSIS: The thermal analysis of the copper carbonate nanoparticles have been investigated using DSC analysis over a temperature of 30-300 0 C. Fig.4 shows the DSC curve of copper carbonate nanoparticles. The melting point can be determined from the melting curve with pure substances; the melting point corresponds to the onset. Impure samples often show several peaks. Substances with eutectic impurities exhibit two peaks; first the eutectic peak whose size is proportional to the amount of impurity and then the main melting point. The downward movement of the peak in DSC heating curve indicates that the peak is endothermic peak. A small low temperature endothermic peak at 158.38 0 C is due to the impurity and a large high temperature endothermic peak at 264.04 0 C in a DSC heating curve is a melting peak. The thermal data in DSC curve of copper carbonate nanoparticles are shown in table.1. Table.1: Thermal data in DSC curve of copper carbonate nanoparticles Sample/Properties Copper carbonate nanoparticles Low temperature endothermic peak High temperature endothermic peak Quantity 4.728mg 4.728mg Heating Rate 10 0 C/min 10 0 C/min Onset 149.6 0 C 256.56C Peak 158.38 0 C 264.04 0 C Endset 165.58 0 C 277.45 0 C 3
Fig.4: DSC curve of copper carbonate nanoparticles 3.3. TGA-DTA ANALYSIS: Thermal analysis of copper carbonate nanoparticles is also carried out by thermogravymetric analysis (TGA) and differential thermal analysis. 16.713mg of copper carbonate nanoparticles at a temperature from 40 C to 830 C at 20 C/minute is analyzed. TGA/DTA thermograms of copper carbonate nanoparticles are shown in fig.5.the thermal analysis data of copper carbonate nanoparticles are shown in table.2. The descending TGA thermal curve indicates a weight loss occurred. The TGA curve represents the single stage decomposition of the sample [3]. The area in the DTA curve is 3757.365mJ and ΔH value is 224.8111J/g and the peak is 276.66 C. The two peaks in TGA curve are 151.93 C and 274.64 C. Fig.5: TGA/DTA thermograms of copper carbonate nanoparticles 4
Table.2:The thermal analysis data of copper carbonate nanoparticles Material Copper carbonate nanoparticles TGA temperature ( 0 C) 151.93 274.64 DSC peak temperature ( 0 C) 158.38 264.04 DTA loss (%) 16.16 13.7 weight 4. CONCLUSION: The copper carbonate nanoparticles have been prepared by chemical co-precipitation method. TEM analysis suggests that the average particle size is 5.7±4.9nm, the standard deviation is 4.9nm and the polydispersity of copper carbonate nanoparticles is 87% and the diffraction rings on SAED pattern matches with the XRD pattern. The DSC curve shows the melting peak. The TGA curve represents the decomposition of the sample in single stage. 5. REFERENCES: [1].M. Samim, N.K. Kaushik, A. Maitra, Effect of size of copper nanoparticles on its catalytic behaviour in Ullman reaction, Bull. Mat.Sci., Vol. 30, 535-540, 2007. [2].R.Hepzi Pramila Devamani and M.Sabeena, Synthesis and Characterization Copper Carbonate Nanoparticles, Golden Research Thoughts, Vol.3, issue 10, 3601-3610, 2014. [3].Tiverios C. Vaimakis, Thermogravimetric Analysis. 5