GRAPHENE OXIDE REINFORCED PORTLAND CEMENT

Seminar Report

on

“GRAPHENE OXIDE REINFORCED PORTLAND CEMENT”

Submitted by

Aniket Subhash Pateriya

Guide

Prof. S. G. Adhau

Submitted to Sant Gadge Baba Amravati University, Amravati in partial

fulfillment of the requirements for the award of degree

BACHELOR OF ENGINEERING

in

CIVIL ENGINEERING

DEPARTMENT OF CIVIL ENGINEERING

PROF. RAM MEGHE INSTITUTE OF TECHNOLOGY AND

RESEARCH, BADNERA, AMRAVATI-444701

2016-2017

PRMIT AND R,BADNERA Page 1

CERTIFICATE OF EXAMINATION

This is to certify that the Seminar Report titled “GRAPHENE OXIDE REINFORCED

PORTLAND CEMENT”, has been satisfactorily completed by Aniket Subhash Pateriya in partial

fulfillment of the award of Degree of BACHELOR OF ENGINEERING in CIVIL ENGINEERING from

Sant Gadge Baba Amravati University, Amravati for the academic session 2016-2017.

Date: 06 / 10/2016 Prof. S. G. Adhau


ACKNOWLEDGEMENT

I would like to express my gratitude to all those who gave me the

opportunity to prepare this seminar report. I would like to thank Prof. S. G. ADHAU For his kind

suggestions, inspiration and guidance during preparation of this seminar report.

I express my deep sense of gratitude towards Prof. P. KADU, Head of Civil

Engineering Department for providing me all the facilities.

Last but not least, this acknowledgement would be incomplete without

rendering any impartial gratitude to all those people who have help me directly or indirectly in

preparing this seminar report.

ANIKET PATERIYA

Final Year B.E.

Civil Engineering Department.

P.R.M.I.T. AND R. ,Badnera


ABSTRACT

In this experimental study, the reinforcing effects of graphene oxide (GO)

on portland cement paste are investigated. It is dis- covered that the introduction of 0.05% by

weight GO sheets into the cement paste can increase the compressive strength and tensile

strength Of the cement composite due to the reduction of the pore structure of the cement

paste.The inclusion of the GO Sheets enhances the degree of hydration of the cement paste.

However, the workability of the GO-cement composite becomes somewhat Reduced. The

overall results indicate that GO reinforcing the engineering properties of portland cement.


INTRODUCTION

Graphene oxide which forms a matrix material that exhibits improved

compressive and flexural strength relative to an equivalent non- graphene oxide

comprising matrix material. They have developed a cementitious matrix with enhanced

strength and durability through the incorporation of graphene oxide (GO). Ordinary

Portland Cement (OPC) is widely used in the construction industry. However, to

overcome its poor tensile properties and to delay the development of micro-cracks, it

must be reinforced with steel bars and various fibers may be added.

Recent advancements in nanotechnology have produced nanosized particles

that could be used as reinforcements to hold back the formation and propagation of micro

cracks at the start. Nano-reinforcements in cementitious matrix materials are more

effective than conventional steel bar reinforcements (at millimeter scale) because they can

control nano-size cracks (at the initiation stage) before they develop into micro-size

cracks.

Recent developments of novel nanosize fibers, such as carbon nanotubes

(CNT’s) and graphene, have opened up new possibilities for improving the strength of

cement paste.As a graphene derivative, graphene oxide (GO) comprises a mono-layer of

sp2 -hybridized carbon atoms the oxygen functional groups, attached on the basal planes

and edges of GO sheets, significantly to change the van der Waals force (intermolecular

forces ) between the GO sheets and therefore improve their dispersion in water. GO also

exhibits high values of tensile strength, aspect ratio and large surface area.


PREPARATION OF GO

Graphite oxide is synthesiz from natural graphite using the modified

“Hummers method”. The graphite powder (0.5 g) is add to an 80 °C solution of

concentrat H2SO4 (23 ml), NaNo3(0.5g). The resulting mixture is cool to room

temperature over a period of 4 h, then carefully add 3g of KMno4. The resulting mixture is

heat to temperature 35 °C over a period of 2 h, then carefully dilut with water, The

resulting mixture is heat to temperature 98 °C over a period of 2 h,then turn off the filter,

and wash until the pH of the filtrate was close to 7 . The mixture is then stirr at room

temperature for 1 h. then add 10 ml of peroxidized to terminate the reaction. Afterwards

the sample is filter and wash with 1 :10 HC1 solution and further wash by water. The

resultant product is ‘graphene oxide’.

Fig (1) Synthesis of GO


Fig (2) Diluted GO solution GO SHEET

CHARACTERISATION OF “GRAPHENE OXIDE REINFORCED

PORTLAND CEMENT”

MATERIALS :-

The OPC Cement Australia, as defined by the AS 3972-2010 (Australian

Standard for General purpose and blended cements).

Graphite, with an average particle size of 44 micron (mesh 325).

GO solution.

Potable water.

METHOD :-

Casting procedures for all samples are similar.

The mixture was then placed into a steel mould of respective size according to

different testing. Each mould was vibrated for 15 to 30 seconds on a vibration

table. All specimens were immediately covered by polyethylene sheets in order to

prevent loss of water from the samples.

After 24 hours, the hardened cement specimen was then demoulded and cured in

a calcium hydroxide bath to prevent lime leaching out from the cement pastes.


For specimens tested at an age of 7 days, 14 days and 28 days. All the specimens

were allowed to dry in the air for 12 hours before they were subjected to

mechanical tests.

Fig (3) 15 cm x 15 cm x 15 cm Cube Fig (4) 15 cm x 15 cm x 80cm Prism

MECHANICAL AND INTERNAL PROPERTY TESTS :-

FLEXURAL STRENGTH:-

Flexural strength is one measure of the tensile strength of cementitious

matrix materials. This test was carried out using a closed-loop MTS servo-

hydraulic testing machine with a 50 KN capacity. The sample was sliced into

small beams measuring 150 mm x 150 mm x 800 mm for the bending test. The

displacement control rate was 0.1 mm/min so that the maximum load for any

specimen was achieved within the first 50 to 90 seconds.

COMPRESSIVE STRENGTH:-

150 mm x 150 mm x 150 mm for the compressive strength test. This test

was carried out using a closed-loop MTS servo-hydraulic testing machine.


Fig (5) MTS servo-hydraulic Fig (6) Point flexural setup

testing machine with LX 500

VERTICAL DISPLACEMENT:-

To verify the leveling of the surfaces of test specimens two linear

voltage displacement transducers (LVDTs) were used to measure the vertical

displacement of the specimen on the left and right sides.

Fig (7) Linear Voltage Displacement Transducers

STRAIN:-

The strain of the specimens was measured by using a laser

extensometer of LX 500. This instrument is specifically designed for accurate,

non-contact measurement of strain on various materials under tensile or

compressive conditions.To obtain the post-peak response of specimens under

compression, the load was applied at a constant displacement rate of 0.4

mm/min. The stress-strain curves were plotted according to the strain measured by

the laser extensometer.


Fig (8) Laser Extensometer of LX 500

ULTRASONIC PULSE VELOCITY MEASUREMENT:-

Ultrasonic pulse velocity was used to detect internal cracks at millimeter

scale. Ultrasonic pulse velocities were measured by a pulse meter PT 400. The principle

of this test involves sending a wave pulse into the specimen and measuring the travel time

for the pulse to propagate through the specimen. Pulses are not transmitted through large

air voids in the paste and, if such a void lies directly in the pulse path, the waves are

deflected around the void and the instrument will indicate the longer time taken by the

pulse to circumvent the void.

Fig (9) Pulse Velocity Measurement PT 400

TEM ANALYSIS:-

A Philips CM20 analytical transmission electron microscope (TEM)

digital CCD camera was used to observe the GO sheet structure. To prepare the


sample a drop of GO solution was spattered (mark made when wet solution hits a

surface) onto a carbon film on 400 mesh Cu grids. Then the grid was left in room

temperature for 24 hours to dry and was used for TEM analysis.

SEM ANALYSIS:-

A JEOL 700 IF FEG high resolution scanning electron microscopy

was used to observe the morphology. The SEM samples were remaining pieces (5

mm x 5 mm x 3 mm) from cube which had been tested under compression.

Fig (10) CM20 Transmission Fig (11) JEOL 700 Scanning Electron

Electron Microscope Microscopy

NITROGEN (N2) ADSORPTION TESTS :-

After the mechanical testing, 10 gram samples of each mix were

collected randomly and grounded to particle sizes in the range of 590 micron

(mesh 30) and 1190 micron (mesh 16). Two samples were used for measuring the

surface area and the pore size distribution of each mix. Nitrogen adsorption and

were carried out using a Micromeritics ASAP 2020 gas adsorption analyzer at

77 K.


Fig (12) ASAP 2020 Gas Adsorption Analyzer

RESULTS:-

SEM image of GO sheets from 0.005 mg/ml aqueous GO solution shown in Fig

(13). According to the SEM image, the sizes of GO sheets are widely distributed

from less than 1 μm to over 200 μm.

TEM image of GO sheets from 2 mg/ml aqueous GO solution. It can be seen that

the grid appears to be entirely filled with the GO sheets. This 'visual' effect is due

to the enormous surface area of the sheet, thereby providing a large interface

between GO sheet and cement matrix.

Fig (13) SEM image of GO sheet Fig (14) TEM image of GO sheet

The wrinkled surface can provide mechanical interlocking between the GO sheet

and the cement matrix, thereby helping to enhance the interfacial load transfer

between the GO sheet and the cement matrix and achieving better bond strength.


By using mini-slump tests, the workability is measured and compared, the

addition of GO sheets leads to a slight reduction in workability.

Fig (15) Geometry of mini-core Fig (16) Slump result by mini-slump

Use in mini-slump test

Test results in Table 1 shows that there were no significant differences in pulse

transmission time between OPC and GO/cement composite, indicating little

entrapment of large air voids even though the GO/cement paste workability was

slightly less than OPC. The good homogeneity is further confirmed by the

enhanced strength of the GO/cement composite.

Table (1) Hardened properties of mixes

*The weight efficiency factor = flexural strength increase / (Additive/Cement) ratio


The weight and dimensions of three beams (15 mm x 15 mm x 80 mm) per mix

were measured in order to calculate the density of a particular mix. The

calculations were carried out in accordance with the requirements of AS

1012.12.1. The density of individual mixes is presented in Table 1. As expected,

the density of the GO/cement composite is similar to that of cement paste. This is

due to a similar density between GO sheets and cement pastes.

The results of compressive strength and flexural strength of GO/cement composite

and plain cement paste are summarized in Table 1. Results show a remarkable

increase in both compressive and flexural strengths. The addition of GO enhances

the compressive strength by 15% to 33% and flexural strength by 41% to 59%

respectively.

Fig (17) stress-strain curves (28 days) Fig (18) volume-pore size curves (28 days)

Elastic modulus and toughness

The stress-strain curves (under compression) for plain cement paste

and GO reinforced composite are shown in Fig (17). The elastic modulus, taken as

the tangent to the stress-strain curve under compression, is summarized in Table 1.

As the weight fraction of GO in the cement paste is only 0.05%, it is of little

surprise then that the elastic modulus of the GO/cement composite is close to that

of the cement paste. A slight increase in elastic modulus (from 3.48 to 3.70 GPa)

may be due to the decrease in the number of original shrinkage cracks owing to

the GO arresting the cracking.


The addition of GO increased the strain corresponding to the peak

stress, indicating an increase in the level of ductility. In this work, the toughness is

measured as the total area under the stress-strain curve (under compression) up to

a strain of 0.004, which is approximately 2 times of the ultimate strain

(corresponding to the peak stress). The values of toughness are summarized in

Table 1. It can be seen that the toughness of GO/cement composite was

significantly increased as compared to the plain cement paste.

GO should have a higher surface adsorption capacity when compared to CNTs.

Adsorption would trap ions (e.g. Ca2+) on the surface of GO, which allows the

initial nucleation reactions to take place, thereby increasing the production of

calcium silicate hydrates (C-S-H). The C-S-H phase contains a network of very

fine pores called gel pores, giving it an extremely high specific surface area, and

making the total surface area of a given cement paste essentially determined by its

C-S-H gel content.

Fig (19) SEM image of sample after 28 days of curing

Above fig (19) showing calcium silicate hydrates (C-S-H) gel in the form of a

dense sponge matrix that gradually spread, merges, and adheres to GO,

strengthening the cement and reducing its permeability by reduce pore size.

To determine the surface area of the GO/cement and OPC samples, N2 adsorption-

desorption measurements, The addition of GO has increased the measured surface

area from 27.3 m2/g to 64.9 m2/g. Indicates that the addition of GO increases the

pore volume of the composites in the pore diameter range of 1 nm - 80 nm. A


similar phenomenon is also observed in CNT reinforced cement composite.

Results also show a significant increase in the volume of small and medium pores

(1 nm - 45 nm) for the composite containing GO sheets. As the pore diameter

increases, the difference in pore volume decreases. In the range of 45 nm to 80

nm, the pore volume of OPC and GO/cement is similar. The small pores (1 nm -

10 nm) are primarily gel pores which were composed of pore system in C-S-H

gel. A high proportion of gel pore is thus an indication that the addition of GO

accelerate the hydration process.

Besides the nucleation effect, the hydration process may be also influenced by

reactions between the carboxylic acid and the C-S-H or Ca (OH)2. Such reactions

are believed to be responsible for the formation of strong covalent bonds between

cement matrix and GO.

ADVANTAGES OF “GRAPHENE OXIDE REINFORCED

PORTLAND CEMENT”:-

Several researchers have found that the addition of CNTs results in little change in

strength or even a deterioration of the composite in some cases. The reasons for

this are generally attributed to the poor dispersion of CNTs and weak bonding

between the CNTs and the cement matrix while the oxygen functional groups,

attached on the basal planes and edges of GO sheets, significantly alter the van der

Waals interactions between the GO sheets and therefore improve their dispersion

in water.

The length of CNTs can be up to centimeters, which gives an aspect ratio

exceeding 1000 while the aspect ratio of a single graphene sheet can reach more

than 2000.

Value of surface area of a single graphene sheet can theoretically reach 2600 m2/g,

which is much higher than those of CNTs.

GO can be easily acquired from natural graphite flakes (inexpensive source).

The ability to improve matrix durability.

To- reduce the quantity of steel reinforcement required in cementitious matrix

structures.


Allow adoption of thinner and lighter concrete structures, allowing for new

architectural designs.

Reduced concrete consumption.

Relatively low weight percentage levels of graphene oxide such as between 0.01%

to 0.5% by weight of the OPC is required.

Resistance too many environmental deterioration attack.

DISADVANTAGES OF “GRAPHENE OXIDE REINFORCED


It reduces the workability.

GO produce when at laboratory level it procedure make it expensive.

APPLICATIONS OF “GRAPHENE OXIDE REINFORCED


Precast products.

Offshore and other structures in marine environments.

Well cementing.

Smart materials for structural health monitoring.

Fig (20) Precast staircase


Fig (21) Marine construction

Fig (22) Well cementing must in

“Geothermal power plant injection well”


Fig (23) GO sheets more sensitive

in concrete for SHM (X ray type)

CONCLUSION:-

This paper reports the influence of 0.05% by weight GO (by weight

of cement) on the workability, degree of hydration, pore structures, and strength of the

OPC paste. The findings can be summarized as follows:

Similar to other nonmaterials, i.e., nanosilica and CNTs, the addition of a small

proportion of GO sheets reduces the workability of OPC.

The use of GO enhanced the degree of hydration of OPC paste.

The addition of GO enhances the compressive strength by 15% to 33% and

flexural strength by 41% to 59% respectively.


The reduction of pore size could be caused by the enhancement in degree of

hydration and hence in reduce the permeability, reduce the formation of micro-

cracks and hence make it more durable structure.

On the basis of “synthesis of GO” it is clear that the production of GO if done in

industrial level (large scale) then it may reduce the initial cost of GO hence it may

excessive use in future to make more safe ,durable and economical construction

based on “graphene oxide reinforced Portland cement” instead of “ordinary

Portland cement”.

REFERENCES:-

“Graphene Oxide as a cement reinforcing additive Preliminary study”, Prof.

Paolo Gronchi , Dott. Luigi Brambilla and Ing. Marco Goisis

“Optimizing content graphene oxide in high strength concrete”, Valles Romero

Jose and Emilio Raymundo

“Graphene oxide reinforced cement and concrete”, Zhu Pan, Wenhui DUAN,

Dan Li and Frank Collins (patent number : WO2013096990 A1)


https://www.google.com/search?tbo=p&tbm=pts&hl=en&q=ininventor:%22Frank+Collins%22

https://www.google.com/search?tbo=p&tbm=pts&hl=en&q=ininventor:%22Dan+Li%22

https://www.google.com/search?tbo=p&tbm=pts&hl=en&q=ininventor:%22Wenhui+DUAN%22

https://www.google.com/search?tbo=p&tbm=pts&hl=en&q=ininventor:%22Zhu+Pan%22

“Reinforcing Effects of Graphene Oxide on Portland Cement Paste”, Asghar

Habibnejad Korayem , Ling Qiu , Frank G Collins and C. M. Wang
