Graphene-MnO2 nano-composite as sensor for structural health monitoring of civil infra structures

Abstract
Electrochemical sensors are involved in the corrosion and structural health monitoring (SHM) of concrete structures. In this investigation, a novel attempt has been made to synthesis Graphene modified MnO2 (GO-MnO2) nanoparticles by chemical method. Synthesized material was characterized by following analytic techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectra and Scanning Electron Microscopy (SEM). The results are clearly indicated that MnO2 nanorods are monodispersed on Graphene surface. Graphene modified MnO2 nanocomposites sensors are fabricated and embedded in concrete structures for corrosion monitoring of reinforced steel. The suitability of the assembled sensor was evaluated by electrochemical tests such as potential stability, sensing ability, reversibility and impedance spectroscopy. GO-MnO2 showed perfect stability for the exposure period upto 30 days. The sensor was embedded in concrete and the studies are under progress.

Materials and method

Synthesis of graphene/MnO2 composites
GO- 0.05g and MnCl2.4H2O (0.27 g) were dispersed in isopropyl alcohol (50 mL), with ultrasonication for 0.5 hr. 85 C Centrifuge at 10,000 rpm for 30 min

KMnO4 (0.15 g) dissolved in 5 mL of DI water was added to the above boiling solution.

The resulting insoluble slime layer of Black color precipitate was formed at the bottom of the flask

Collected particles

Analytical characterization FT-IR, Raman spectra, XRD pattern, SEM-EDAX TEM

Results and discussion

FTIR spectra

Raman spectra

XRD

SEM EDAX observation

cps/eV 7

a)

MnO2)
C O Mn Mn

0 2 4 6 keV 8 10 12 14

cps/eV

b)

GO-MnO2)
C O Mn Mn

In the FT-IR spectrum of GO (Fig. 3a), stretches of OH, C-O, it can be assigned to Graphene sheet. In addition, two broad absorption bands can be found at 618 cm1 and 515 cm1, which are associated with the coupling mode between Mn-O stretching modes tetrahedral and octahedral sites.

Raman spectra of MnO2 and GO-MnO2 are shown in Figure. From the relative intensities of the D and G band peaks at 1350 and 1590 cm 1, it can be concluded that the size of the sp2 domains increases during reduction of GO. Moreover, the similar MnO2 peak at 621.41 cm 1was observed both samples.

Fig shows the XRD pattern of MnO2 and GO-MnO2 were obtained by simple chemical method. These diffraction peaks of synthesized MnO2 and GO-MnO2 were similar to tetragonal crystal phase of MnO2 (JCPDS; 65-2821) and moreover high intensity peaks of GO at around 2= 11.2 and 27,2 corresponds to the (001) and (002).

0 2 4 6 keV 8 10 12 14

TEM observation

Fabrication of sensors and characterization

The morphology of the as synthesized MnO2 and GOMnO2 nanostructure is shown in Fig. Fig a is an bright field TEM image of the MnO2 nanorod. These image show well dispersed nanorods the diameter of the individuals nanorod are in the range of 10-20 nm their length are 0.1 to 0.2m. Moreover, higher magnification of TEM image of the MnO2 nanorods , to observed two lattice fringe with a d-spacing of 0.32nm and 0.71nm, corresponds to 101 and 111 of MnO2 crystal plane which is coincide with XRD data and SAED diffraction. In comparing Fig. (a) and (b), it can be clearly seen that GO-sheet have been decorated with nanorods MnO2 structure. More over, the edge of the graphene sheet represented the TEM image. There is no significant observed that morphology of the MnO2 nanorods. The similar MnO2 lattice fringe was observed on the GOMnO2 nano composite. Morphological study revealed that the MnO2 nanorod crystal growth on the graphene sheet.

a)

b)

a)

b)

a) TEM image of the MnO2 nanorod and (b) GO-MnO2 nanocomposite

A structure of GO-MnO2 electrode.

Stability test for MnO2 and GO-MnO2 sensor in concrete environments

a) Cyclic polarization curve and Impedance plot (b) for GO-MnO2 sensor embedded in concrete environments.

Corrosion monitoring by embedded Sensor in concrete structures

Table. Polarizations parameters for rebar embedded in concrete with respect to embedded sensor and surface mounted electrode System
Embedded (corrosion rate sensor) MnO2 GO-MnO2 -585 Surface mounted -376 0.00025 0.0001802 0.00287 0.00208

Conclusions
In the present study, MnO2 nanorod success fully crystal growth on the graphene sheet by simple chemical method. The synthesized GO-MnO2 was confirmed by Raman spectra, XRD, SEM-EDAX and TEM. The resultant products were fabricated by embeddable potential sensor in concrete structures for corrosion monitoring. The stability of sensor in concrete was found to be constant throughout the exposure period of one month at high alkaline medium. Electrochemical studies revealed that GO-MnO2 embeddable sensors always showed higher half-cell potential values than surface mounted electrodes. This is due to the IR drop problem on measuring the Half-cell potential. Polarization study concluded that, embeddable sensor showed higher Ecorr values than surface mounted electrodes. This is quite suited for our interest to recommend GO-MnO2 sensor is a more reliable sensor for concrete. This behavior is quite suited to perform as an ideal sensor working under any environmental conditions.

Ecorr (mV)
-402

Icorr(mA.cm2)
0.0002258

Corrosion rate /(mmpy)

0.002617

Sensors assembled in concrete structures

Half-cell potential of rebar embedded in concrete cube with respect to embeddable sensor and surface mounted electrode

Potentiodynamic polarization curves for steel in concrete (a). Embedded sensor (b).Surface mounted electrode

Acknowledgement
The authors thank to ESC-0110 Project for financial support

*Corresponding author: corrosaras@gmail.com