Effect of Carbon

Nanomaterials Embedded in a Cementitious Matrix

CLARISSA ROE, BRITTANY BRODER, JASON WILSON,

DR. EDWARD KINTZEL, DR. KEITH ANDREW

Introduction

Background Information/Assumptions

Experiment

Images and Results

Conclusions

Future Plans/Improvements

Why?

Purpose: To see if carbon nanofibers have an

effect on the splitting tensile strength of small

gypsum columns.

Assumption 1: The more aggregate present in the

sample, the lower the splitting tensile strength.

Assumption 2: The more area of additive in

contact with cement, the stronger the product

will be.

Assumption 3: The more rounded the additive is,

the weaker the final product will be.

Materials Available

Hydro-Stone Gypsum Cement

Carbon Nanofibers (CNF)

Single Walled Carbon Nanotubes

(SWNT)

Buckminsterfullerene (C60)

Graphene Oxide (GO)

Single Walled Carbon Nanotubes

Diameter: 0.7 to 1.4 nanometers.

Compared to Cement?

Compressive Strength

Hydrostone gypsum cement: 10,000 psi or

0.06895 GPa (Ultracal- 0.047- 0.054 GPa)

Single strands of SWNT : 40.6 GPa

Tensile Strength

Steel: 0.51-0.62 GPa

CNT: 13-52 GPa

Ultracal gypsum cement: (dry) .046-.050 GPa

Retrieved from: http://www.nanocomptech.com/what-are-carbon-

nanotubes

C60 and Graphene Oxide

C60 Young’s Modulus

C60 : 20 ± 5 GPa

Gypsum cement- 1.45- 1.72 GPa

Graphene Oxide (GO) Sheets

Average tensile strength- 24.7 ± 4.5 GPa

Steel: 0.51-0.62 GPa

Ultracal gypsum cement: (dry) .046-.050 GPa

C-60 image retrieved from: http://www.jameshedberg.com/scienceGraphics.php?sort=all&id=c60-buckyball-atoms-red

Graphene Oxide image retrieved from:

http://www.sigmaaldrich.com/catalog/product/aldrich/763713?lang=en&region=US

Experiment

Part I- Gypsum Discs (all concentrations)

Imaged discs with varying concentrations of CNF

Part II- Gypsum Columns (bolded concentrations)

Gathered splitting strength data

Imaged discs

CNF CNF % by mass

SWNT 0.1 0.2 0.4 0.6 0.8 1.0

C60 0.1 0.2 0.4 0.6 0.8 1.0

Graphene Oxide 0.1 0.2 0.4 0.6 0.8 1.0

Part I- Gypsum Discs

SWNTC60Graphene Oxide

Blanks (1 mm thick, 2:1 cement: water)

Images: Carbon Nanotubes- 0.2% (3k x)

C60- 0.2% (3k x)

GO- 0.8% (3k x)

Part II- Gypsum Columns

Sample sizes = ~ 2 in (5.08 cm) height, ~ 1 in (2.54

cm) diameter

3.1:1 ratio of cement to water (0.32 water:

cement)

?

Prep Cont.

Mixed for ~3 minutes

Vibrated ~30-60 seconds

Cured for 3 days

Images of Samples- BlanksFreshly Made Samples

Ready for Testing

CNF Samples

C60- Dry 0.8%

C60 - Fresh 0.8%

GO- Dry

0.8%

GO- Fresh 0.8%CNT- Fresh 0.8%

CNT- Dry 0.8%

Splitting Tensile Strength

Blanks samples broke within 34-42 seconds. CNT samples broke within

1 min, 30 seconds.

Cracked SamplesSample 1G- BLANK

CNT- Sample 2’-1- 0.8%

C60 - Sample 4’-2- 0.8%GO- Sample 6’-1- 0.8%

Images: Blanks (3k x)

Sample 2A-2: 0.1% CNT (2k x)

12

4

3

Sample 3B-3: 0.1% C60 (1k x)

1

2

3

Sample 5’-1: 0.1% GO (1.2k x)

Average S.T.S of CNT in psi

a = 600 ± 30 (psi)

b = -(30 ± 8) *103 (psi/concentration)

250

300

350

400

450

500

550

600

650

0.0% 0.1% 0.2% 0.3% 0.4% 0.5% 0.6% 0.7% 0.8% 0.9%

Ave

rag

e S

plit

tin

g T

en

sile

Str

en

gth

(p

si)

CNT Concentration (%)

509.3

570.4

527.5

304.3

Average S.T.S of C60 in psi

a = 500 ± 8 (psi)

b = -(1 ± 2)*103 (psi/concentration)

250

300

350

400

450

500

550

600

650

0.0% 0.1% 0.2% 0.3% 0.4% 0.5% 0.6% 0.7% 0.8% 0.9%

Ave

rag

e S

plit

tin

g T

en

sile

Str

en

gth

(p

si)

C60 Concentration (%)

509.3 501.3 484.1492.8

Average S.T.S of GO in psi

a =500 ± 40 (psi)

b =-(7 ± 9) x 103 (psi/concentration)

250

300

350

400

450

500

550

600

650

0.0% 0.1% 0.2% 0.3% 0.4% 0.5% 0.6% 0.7% 0.8% 0.9%

Ave

rag

e S

plit

tin

g T

en

sile

Str

en

gth

(p

si)

Graphene Oxide Concentration (%)

509.3

572.7

450.8471.0

Percentage Change of Strength

of CNF Samples vs. Blanks

CNF Concentration (%) SWNT vs.

Blanks (%)

C60 vs.

Blanks (%)

GO vs.

Blanks (%)

0 0 0 0

0.1 11.9 -1.6 12.4

0.2 3.6 -4.9 -11.5

0.8 -40 -3.2 -7.5

• Positive percentage values indicate an increase in strength

• Negative values indicate a decrease in strength.

• The addition of SWNT resulted in more increases in strength, while

the addition of C60 resulted in more decreases in strengths.

Conclusions

CNT- As more SWNT were added, the weaker the concrete

became.

SWNT exhibited more of the expected behavior of aggregates

in cementitious materials.

C60- As more C60 was added, the strength did not

drastically change.

GO- As more GO added, the weaker the concrete

became, though not as drastically as CNT.

Future

Plans/Improvements Improvements

More samples

Better quality gypsum. A different batch of Hydrostone gypsum could yield different results. Ultracal is more consistent.

Use Portland Cement, as that is the most common concrete ingredient and would have more applications

More effective/ consistent preparation methods and curing environments

Future Plans

Possible gypsum has been found on Mars. Research could be done to see if gypsum could be used in structure formation.

Cost Analysis

Homeland Security

Connection

Assist in rebuilding of natural disaster sites

Protection from natural disasters (earthquakes,

fires, etc.) and terrorism (bombings, crashes, etc.)

by improving building materials

References Atteberry, J. (2016). How Does a Scanning Electron Microscopes Work Its Magic? PREVNEXT. Retrieved March 12, 2016, from http://science.howstuffworks.com/scanning-

electron-microscope3.htm-

AZoM.com (2016, July 20). Properties: Stainless steel - grade 304 (UNS S30400). Retrieved July 25, 2016, from http://www.azom.com/properties.aspx?ArticleID=965

Cao, C., Daly, M., Singh, C. V., Sun, Y., & Filleter, T. (2015). High strength measurement of monolayer graphene oxide. Carbon, 81, 497–504. doi:10.1016/j. carbon.2014.09.082

Cunningham, C., Townsend, F., & Fagundo, F. (1983-1984). The Development of Micro-Concrete for Scale Model Testing of Buried Structures. Engineering and Services Laboratory Air Force Engineering and Services Center. Retrieved April 10, 2016.

Cole, S., Buis, A., & Webster, G. (2011, December 7). NASA mars Rover finds mineral vein deposited by water. Retrieved July 16, 2016, from http://www.jpl.nasa.gov/news/news.php?release=2011-377

Department of Homeland Security. Ensure Resilience to Disasters. Retrieved November 9, 2016, from https://www.dhs.gov/building-resilient-nation

Department of Homeland Security. Prevent Terrorism and Enhance Security. Retrieved November 9, 2016, from https://www.dhs.gov/prevent-terrorism-and-enhance-security

Energy-dispersive detector (EDS). (n.d.). Retrieved April 12, 2016, from http://serc.carleton.edu/research_education/geochemsheets/eds.html

Environmental Protection Agency. (2004). Sector Strategies Performance Report. Retrieved April 5, from https://archive.epa.gov/sectors/web/pdf/performanceclr.pdf

Gong, K., Pan, Z., Korayem, A. H., Qiu, L., Li, D., Collins, F., . . . Duan, W. H. (2015). Reinforcing Effects of Graphene Oxide on Portland Cement Paste. J. Mater. Civ. Eng. Journal of Materials in Civil Engineering, 27(2). doi:10.1061/(asce)mt.1943-5533.0001125

Grdic, Z., Toplicic-Curcic, G., & Stojic, N. (2010). Concrete aggregate and cement mass content effects on compressive strength. Facta universitatis - series: Architecture and Civil Engineering, 8(4), 413–423. doi:10.2298/fuace1004413g

Gypsum Association, (2013, December 10). Gypsum through the ages. Retrieved July 15, 2016, from https://www.gypsum.org/about/gypsum-101/history-gypsum/https://www.youtube.com/watch?v=3fYlKUUyj4M)

Harris, H. G., & Sabnis, G. M. (1999). Structural modeling and experimental techniques. Boca Raton: CRC Press.

Hoen, S., Chopra, N. G., Xiang, X.., Mostovoy, R., Hou, J., Vareka, W. A., & Zettl, A. (1992). Elastic properties of a van der Waals solid: C 60. Physical Review B, 46(19), 12737–12739. doi:10.1103/physrevb.46.12737

Kumar, S., Kolay, P., Malla, S., & Mishra, S. (2012). Effect of Multiwalled Carbon Nanotubes on Mechanical Strength of Cement Paste. Journal of Materials in Civil Engineering, 24(1), 84–91. doi:10.1061/(asce)mt.1943-5533.0000350

Mixing Instructions. (n.d.). Retrieved April 3, 2016, from http://plaster.com/mixing.html

Modulus of elasticity or young’s Modulus - and tensile Modulus for common materials. Retrieved July 15, 2016, from http://www.engineeringtoolbox.com/young-modulus-d_417.html

Reference (Cont.) Nanocomp Technologies | Nanotechnology. (n.d.). Retrieved April 4, 2016, from http://www.nanocomptech.com/what-are-carbon-nanotubes

Nemati, K. M. (2015, January 3). Aggregates for Concrete. Retrieved November 9, 2016, from http://courses.washington.edu/cm425/aggregate.pdf

Portland Cement Association, (2015). Concrete cracks- A shrinking problem. Retrieved July 15, 2016, from http://www.cement.org/for-concrete-books-learning/materials-applications/architectural-and-decorative-concrete/focus-on-floors/concrete-shrinkage (https://www.usg.com/content/dam/USG_Marketing_Communications/united_states/product_promotional_materials/finished_assets/usg-gypsum-misconceptions-white-paper-en-IG1847.pdf)

Preparation and Mechanical Properties of Graphene Oxide: Cement Nanocomposites. (n.d.). Retrieved April 2, 2016, from http://www.hindawi.com/journals/tswj/2014/276323/

SABNIS, G. M., & WHITE, R. N. (1967). A Gypsum Mortar for Small-Scale Models. ACI Journal Proceedings, 64(11), . doi:10.14359/7606

Scanning Electron Microscope. (n.d.). Retrieved March 12, 2016, from https://www.purdue.edu/ehps/rem/rs/sem.htm

Sideri, S. (2014). Feasibility study of functionalized graphene for compatibility with cement hydrates and reinforcement steel (Unpublished master's thesis). CHALMERS UNIVERSITY OF TECHNOLOGY. doi:http://publications.lib.chalmers.se/records/fulltext/215326/215326.pdf

Sigma Aldrich. (2016). Carbon nanotube, single-walled. Retrieved July 25, 2016, from http://www.sigmaaldrich.com/catalog/product/aldrich/724777?lang=en&region=US

Size and Scale. (n.d.). Retrieved April 4, 2016, from http://education.mrsec.wisc.edu/36.htm

The Effect of Aggregate Properties on Concrete. Retrieved November 9, 2016, from http://www.engr.psu.edu/ce/courses/ce584/concrete/library/materials/aggregate/aggregatesmain.htm

Tokushi Kizuka, Kazuma Saito, Kun’ichi Miyazawa, Young’s modulus of crystalline C60 nanotubes studied by in situ transmission electron microscopy, Diamond and Related Materials, Volume 17, Issue 6, June 2008, Pages 972-974, ISSN 0925-9635, http://dx.doi.org/10.1016/j.diamond.2008.02.038 (http://www.sciencedirect.com/science/article/pii/S0925963508002227)

Ulloa, E. (2013). Fullerenes and their Applications in Science and Technology. Introduction to Nanotechnology. Retrieved March 29, 2016, from http://web.eng.fiu.edu/~vlassov/EEE-5425/Ulloa-Fullerenes.pdf

USG. (2014, April 29). HYDRO-STONE® Gypsum Cements. Retrieved from https://www.usg.com/content/dam/USG_Marketing_Communications/united_states/sds/usg-hydro-stone-gypsum-cement-sds-en-52000000012.pdf

Zu, M., Lu, W., Li, Q., Zhu, Y., Wang, G., & Chou, T. (2012). Characterization of Carbon Nanotube Fiber Compressive Properties Using Tensile Recoil Measurement. ACS Nano,6(5), 4288-4297. doi:10.1021/nn300857d

Yu, M.-F., Files, B. S., Arepalli, S., & Ruoff, R. S. (2000). Tensile Loading of Ropes of Single Wall Carbon Nanotubes and Their Mechanical Properties. Physical Review Letters, 84(24), 5552–5555. doi:10.1103/physrevlett.84.5552

Why Gypsum?

Increased resistance to fire when used in gypsum

boards

Gypsum > Portland Cement for several reasons:

No shrink cracks- Common with regular concrete, when

cement becomes concrete, it loses water and as a result,

a decrease in its volume. This leads to cracking in the

material and will allow other structural problems to occur.

Expand into any crevice it can find and will secure itself to

that space. This allows the user to avoid having to create

crevices.

Gypsum uses water only for hydration and will set evenly.

This is unlike calcium aluminate cement or Portland

cement, where an uneven thickness in the pouring of the

cement will result in uneven drying and shrinkage.

AVERAGE SPLIT TENSILE STRENGTHS

AND UNCERTAINTY FOR SWNT

COLUMNS

CNF Concentration (%) Average S.T.S (psi) Uncertainty (psi)

0 509.3 40.1

0.1 570.4 35.3

0.2 527.5 23.5

0.8 304.3 27.2

AVERAGE SPLIT TENSILE STRENGTHS

AND UNCERTAINTY FOR C60

COLUMNS

CNF Concentration (%) Average S.T.S (psi) Uncertainty (psi)

0 509.3 40.1

0.001 501.3 101.0

0.002 484.1 45.8

0.008 492.8 45.3

AVERAGE SPLIT TENSILE STRENGTHS

AND UNCERTAINTY FOR GRAPHENE

OXIDE COLUMNS

CNF Concentration (%) Average S.T.S (psi) Uncertainty (psi)

0 509.3 40.1

0.001 572.7 38.9

0.002 450.8 49.0

0.008 471.0 21.8

Percent Change Between the

Average Strengths of the CNF

Samples

CNF Concentration (%) SWNT vs. C60 (%) SWNT vs. GO (%) C60 vs GO (%)

0 0 0 0

0.1 13.8 -0.42 -12.5

0.2 8.9 17.0 7.4

0.8 -38.2 -35.4 4.6

• Positive values indicate an increase in strength

• Negative values indicate a decrease in strength.

• The addition of SWNT resulted in an approximately 14% stronger

sample than the C60, but a 0.42% decrease in strength when

compared to GO.

• The choice of which CNF is appropriate for usage depends on the

magnitude of the increase/decrease and how much CNF would

need to be added.

Electron Dispersion

Spectroscopy

• EDS detects x-rays,

absorbs the

energy, and

initiates an

electrical charge.

• Note that carbon

is on the lower end

of the spectrum.

Image obtained from http://amptek.com/wp-content/uploads/2013/12/lew_8.png

Scanning Electron

Microscope

Instead of light, electrons to produce an image.

Better than traditional microscopes

Better sample focus

More ability to control the magnification due to

electromagnets instead of lenses

Higher resolution.

Allows more of a sample to be imaged.

How Does It Work?

Electrons are emitted from the electron gun and travel downward towards the sample.

Electron beam passes through multiple electromagnetic lenses and can be focused on a particular spot on the sample.

When the electron beam hits the sample, it interacts with the sample electrons and causes three types of emissions- secondary electrons, backscattered electrons, and X-rays.

Specific detectors, located towards the bottom of the figure, attract the emissions and depending on the intensity, can produce various shades of black and white images corresponding to the elemental composition of the sample.

Image retrieved from: https://www.purdue.edu/ehps/rem/rs/sem.htm-

Emissions

Images retrieved from: http://www.seallabs.com/how-sem-works.html and http://www.seallabs.com/how-sem-eds-works.html

Why Splitting Tensile

Strength (S.T.S)?

Cement structures have a large compressive

strength, but low tensile strength.

S.T.S provides data that illustrate the carbon

nanofibers bridging across the cement mixture

Related to compression, but gives more

applicable data.

After a 28-day curing period, the addition of

0.03% by mass GO sheets increased the compressive strength of OPC by 46% and the split

tensile strength by 50%.

External Comparisons

(SABNIS & WHITE, 1967)

a =400 ± 50 (psi)

b =-70 ± 50 (psi)

a= (400 ± 40) psi

b= (-70 ± 50) psi

a =300 ± 20 (psi)

b =-30 ± 30 (psi)

0

50

100

150

200

250

300

350

400

450

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Sp

littin

g T

en

sile

Str

en

gth

(p

si)

Aggregate/Gypsum Ratio

0.3 (W/G)

0.35 (W/G)

0.4 (W/G)

A, AB, and B correspond to different points on the granulometric curve.

Percent passing through vs. size of aggregate

Rounded is better than crushed because crushed

stones have more angles and lengths, which allow for better bonding characteristics, but need

more cement paste for a decent mixture.