Journal Paper

Title: Understanding the effect of thermal conductive nanomaterials on composite laminate selfhealing efficacy
Student Name: Stefano Gazzola
Student Email: s3379510@student.rmit.edu.au
First Supervisor Name: Dr. Everson Kandare
Second Supervisor Name: Dr. Shuying Wu

Abstract
In today’s modern battlefield, the limiting factor in a soldier’s defences is his amour
Traditional body armour/ballistic protection systems utilise Kevlar ® due to its relatively high
strength-to-weight ratio, its cost effectiveness and its non-brittle nature. While they do stop a small
portion of small arms fire, the often resultant broken ribs, winding (Solar Plexus Syndrome)
and, in some cases internal bleeding, raises the question of the effectiveness of the amour.
There is also the issue of repeatable usage as once the plate has been damaged the structural
integrity of the composite has been compromised. Self-healing polymers, along with
nanotechnology offers a promising future to help improve ballistic protection.

Keywords: Ballistic, Kevlar, self-healing, nanomaterials

1. Introduction
Aramid fibres such as Kevlar® have
traditionally been used as the material of
choice for ballistic protection, as the fibres
are made of individual filaments, which
cause it to undergo fibril breakage during
impact. Along with this is the high
strength-to-weight ratio that Kevlar®
exhibits, making it a cost effective choice
when compared to some of the other

alternatives, such as steel or titanium
plating.
However the problem with Kevlar is
that it is heavy and cumbersome. Along
with this is also the issue of repeatable
usage, as once the fibres are damaged it
can no longer transfer any loading
throughout the surrounding material, a
phenomena known as fibre bridging. This
reduces the effectiveness of the plate for
potential subsequent impacts or stresses.

However long term heat exposure can also affect the self-healing ability of the EMAA. 280MPa and 75GPa respectively for a unidirectional laminate with a 60% fibre volume fraction content. the mendable polymer EMAA (poly (ethylene-co-methacrylic acid)). The matrix in region 1 and 2 fails due to the load exerted exceeding the materials upper limit. resulting in matrix cracking which typically leads to delamination in mode II. thus increasing the number of rounds the vest can absorb.. These in-plane compression waves travel throughout the throughthickness direction of the composite. it has higher delamination strength then Kevlar. 2011) The fibre also has problem bonding with polymer matrixes due to its oriented chain structure and its skin-core heterogeneity. Studies . and as a result its interfacial strength is only approximately half of glass or carbon fibres. resulting in compression of the secondary yarns. resulting in lower adhesive strength between it and epoxy. 1200MPa. also known as region 1.5N and 31. endure tensile loading/strain. will be used as the self-healing polymer because of its ability to form strong adhesion with the epoxy via hydrogen and covalent bonding (T. 2012).N.(Seung-Chul Kim. much like human skin. 2012). 2011). This causes a weakening in the Kevlar/epoxy interface. compared to Kevlar which is approximately 1300MPa. which is known as region 2. delamination and matrix cracking. 2011) (P. tensile deformation. This is due to the fibres breaking in filaments. 2009) While carbon-fibre also undergoes fibre damage. Reis. (Seung-Chul Kim. Therefore in order to combat this damage. which is used to reverse the damage used by “reverse covalent and/or non-covalent bonding” in order to rejoin the damaged layer. Damage during a high speed impact consists of: compression. This. If the force exerted by the projectile exceeds the shear plug force the rear face of the plate experiences conical deformation. which results in a lower delamination strength then carbon/epoxy.B. rather than clean cracks such as carbon fibre. being in the magnitude of 1500MPa. and 135GPa. shear plugging. Interfacial strength is important during ballistic impact due to the stresses that both the fibre and the matrix have to overcome. carbon/epoxy will be used as it has higher tensile and compressive strength and Young’s modulus. The problem with Kevlar ® and other fibre-reinforced laminates is that they are susceptible to delamination cracking. and any fibres that have not been damaged in shear plugging. which is cracking or splitting between the various plies or layers. 2013) Therefore in order to remedy the issue of fibre damage and its mechanisms. typically in the form of thermal energy.3N respectively (Seung-Chul Kim. The self-healing polymer is used to increase the ballistic absorption by healing over previous damage. It is considered a mendable polymer due to its need of an external stimuli to ‘heal’. with the max mode I load average for carbon/epoxy and Kevlar/epoxy being 79. (Shaktivesh. Compression of the fibres occurs directly beneath the impact region. Yang. and the epoxy can no longer act as a stress transfer mechanism. (Anon. in theory will reduce the damage that the round causes on both the wearer and the plate itself.

which require low energy to reform.” The elastic response the polymer enables it to recoil and the viscosity of the polymer induces final sealing (Diana Döhler.A . as these provide the pressure required to propel the EMAA into the crack. An interesting feature of EMAA is that during high speed (ballistic) impact. 2013).com/catalog/pr oduct/aldrich/426628? lang=en&region=AU} (CH2CH2)x[CH2C(CH3)(CO2H)]Y Figure 1-2: Chemical structure of E. to create a surface that is resin and EMAA rich. show that 5minutes at 150°C provided the maximum adhesive strength between EMAA and epoxy. EMAA works by forming small bubbles that occur post curing of the resin. 2011). The EMAA. Figure 1-1: Chemical structure of EMAA {Image courtesy from http://www. which melts at the high temperatures. Once the hole has been created. The long term efficacy of the healing ability is dependent on the amount of volatiles (chemical groups which make the EMAA) remaining encapsulated within the thermoplastic.M. it begins to seal over. During damage such as impact. the transfer of kinetic energy and friction can actually provide enough thermal energy to repair the polymer in real time (Ming Qiu Zhang.M.conducted by. the remaining strength of the polymer is dependent on “continuing inter-diffusion processes. crystallisation as well as longterm relaxation of polymer chains. the bubbles will burst during crack expansion. This occurs by the hydrogen (polar groups). Should the volatiles escape/diffuse out of the thermoplastic. then flows into the crack plane via microscopic bubbles that swell during post-curing. this will result in lower pressure and reduce the efficacy of the self-healing.sigmaaldrich. and rebind the opposing sides of the fractured epoxy surfaces.

d. CNF which are essentially graphene plates. which is why during the curing phase of composite materials such as carbon-fibre there is such a long dwell time in an autoclave. which will also decrease the chances of thermal damage to the composite. The optimum blend was 9010%wt of epoxy to PCL and containing 0.2%wt CNFs which gave almost double the flexural strength and toughness. along with high tensile strength . n. reducing the mechanical properties of the fibre reinforce polymer composite. METHODS The aim of the project will be to test the mechanical properties such as stiffness and strength in both tensile and compressive loading. (POLYTEC GmbH. Long term exposure to heat can cause oxidation to the epoxy matrix.. CNF content (Zhang et t al. The mixture will then be layered on the carbon-fibre prepreg in a mesh pattern. three specimens will be fabricated. (Zhang et t al. However the main emphasis will be on testing the impact performance of carbon-fibre prepreg with carbon nanofibres that will be embedded in a self-healing polymer.. and also if using CNFs will decrease the regeneration time of selfhealing materials by increasing thermal conductivity. This will show whether or not the SHPs improve mechanical performance of carbon prepregs. 2012).The use of carbon nanofibres (CNF) in the experiment is used to increase thermal conductivity in between the various plies and the epoxy and EMAA matrixes. and repeated for each ply. 2012) Figure 1-3: Flexural and Toughness increase VS. This is due to the insulating properties of thermosetting polymers such as epoxy. a carbon-fibre prepreg without SHPs and CNF. that are stacked on top of each other. In order to assess the improvement of using self-healing polymers and carbon nanofibre.. (Zhang et t al. a carbon-fibre prepreg with SHP but no CNFs and lastly a carbonfibre prepreg with both SHPs and CNFs. CNF content. have a high in-plane thermal conductivity.Studies have shown that CNFs can improve the in-plane and throughthickness thermal conductivity in carbon fibre reinforced composites (CFRP) by approximately 33%.). 2012) Figure 1-4: Tensile strength and Hardness VS. while preserving 78% of the self healing efficiency. . 2. Research has shown that embedding CNFs into SHP such as poly (ecaprolactone) (PCL) can improve mechanical performance without sacrificing the SHP healing efficacy.

to test the polymer’s ability to heal during ballistic events. However the CNF will need to be embedded into the self-healing polymers and made sure that they are evenly dispersed and are oriented in the same direction.2. This process was repeated 3 more times to create 4. 2012) (ASTM International. then using piano hinges to pry open the material. The process for making the carbon/epoxy laminate is as follows: four plies of unidirectional carbon fibre epoxy prepreg were laid up together at 0° before being debulked. two batches of samples will need to be manufactured to satisfy ASTM standards for both tests. 2012) 3. The standards for the DCB tests and impact tests are (ASTM International. This involves the test specimen being held in a set of jaws while a weight is dropt vertically. These were then laid up to form a 16 layer laminated before being debulked for a final time. These will be between 0.1 to 2 percent CNF per unit volume. At each of these percentages.1. The DCB test involves inducing a split in the laminate by inserting a non-adhesive material such as Teflon which must not exceed 13μm in thickness (ASTM International. The material will be tested for different percentages by volume for the carbon nanofibres. neither the carbon nanofibres nor the self-healing polymer will need to be created as these will be purchased. 2013) Once the samples have been created. Results No testing has been started however the DCB testing for the controlled carbon/epoxy specimen will commence on the 12th of June. 4 ply laminates. the length of the crack propagates along the material. 2013). the higher the force needed to pry open the material. and then tested for their mechanical properties. Manufacturing and Testing In the manufacturing phase. (ASTM International. they will be tested using two methods will be used the first being the Double Cantilever Beam (DCB) test. The laminate was then cured in an autoclave at 150°C. . The second method of testing will be a low speed impact test. The stronger the bonds in the material.

engineeringtoolbox. J. Binder. Measurement of Composite Heat Damage.d. 2012. J. S.. F. ASTM International. 2013.pdf [Accessed 28 03 2015]. BASICS OF SELF . INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING. M.l.:John Wiley & Sons.. Composite Structures. 760. 2011. R. ASTM International. a.html [Accessed 27 03 2015]. 1995. 2012. a. Kevlar and Their Hybrid Fibers. n. Impact response of Kevlar composites with filled epoxy matrix. [Online] Available at: http://www.. Volume 94. West Conshohocken: ASTM International. s. J..com/fileadmin/user_uploads/Solutions/Spektroskopie/Documents/PH_A2 _compositeappnoteword.HEALING: STATE OF THE ART. B. P. . a. Performance Composites. Diana Döhler. M.. M. Anon.-J. In: W. R. Y. First ed. Standard Test Method for Mode I Interlaminar Fracture Toughness of Unidirectional Fiber-Reinforced Polymer Matrix Composites. ed. .Bibliography Anon. 321-329. H. R. [Online] Available at: http://www..com/engineering-materials-propertiesd_1225. [Online] Available at: http://www. P. pp. Z.l. Seung-Chul Kim. H. W. LORENTS. MECHANICAL AND THERMAL PROPERTIES OF CARBON NANOTUBES. the engineering toolbox.B. pp. s. Self-Healing Polymers: From Principles to Applications. S. pp..N. 12(2). Standard Test Method for Measuring the Damage Resistance of a Fiber-Reinforced Polymer Matrix Composite to a Drop-Weight Impact Event. Principles of Self-Healing Polymers. 2011.d.:Wiley-Vch . S. 2013.performancecomposites. Experimental and Numerical Investigations of Mode I Delamination Behaviors of Woven Fabric Composites with Carbon.. n. P. R.polytec. 2009.. D.com/carbonfibre/mechanicalproperties_2. K. .asp [Accessed 13 05 2015]. In: Self-Healing Polymers and Polymer Composites. Reis. West Conshohocken: ASTM International. POLYTEC GmbH. 3520-3528. Ming Qiu Zhang.

A. and Velu. J.833-846. International Journal of Impact Engineering. 12(2). AND NAIK. MEURE. pp. Yang. N. Acta Materialia. N. 51. MOHAN.4312-4320 Poly[ethylene-co-(methacrylic acid)] Healing Agents for Mendable Carbon Fiber Laminates In-text: (Meure. Wu and Furman. pp. Polyethylene-co-methacrylic acid healing agents for mendable epoxy resins. K. S. (2013). 833-846. S. Composites Science and Technology. pp.. H. Materials and Design. Experimental and Numerical Investigations of Mode I Delamination Behaviors of Woven Fabric Composites with Carbon. C. 321-329. Sesha Kumar. Y. Toughening and self-healing of epoxy matrix laminates using mendable stitching. S. Y. . N. and Furman. H. 2013) Bibliography: Shaktivesh. S. AND VELU.164-176. pp.. 57(14). NAIR.. Shaktivesh.. 2009) Bibliography: Meure. 2011. pp. C. 2013. Polyethylene-co-methacrylic acid healing agents for mendable epoxy resins In-text: (Meure. Nair. S. T.. N.. pp.. Materials & Design. S. S. 1396-1401. Ballistic impact performance of composite targets. 63.-J. a. D. (2009). (2014). Kevlar and Their Hybrid Fibres. Wu. AND FURMAN. M. Ballistic impact performance of composite targets In-text: (Shaktivesh et al. SHAKTIVESH. WU.. S. S. N. Ballistic impact behaviour of unidirectional fibre reinforced composites. SESHA KUMAR. S. C. Volume 72. S.. J. Ballistic impact behaviour of unidirectional fibre reinforced composites In-text: (Mohan and Velu. D. Furman and Khor. Ballistic impact performance of composite targets. N. 2010) . W. C. and Naik. 2014) Bibliography: Mohan. N. INTERNATIONAL JOURNAL OF PRECISION ENGINEERING AND MANUFACTURING. Volume 51. 2012.Seung-Chul Kim. N. K. Z.

J. (2013). Niu. M. and Altan. AND FURMAN.. NIU... T. D. (2013). J. (2012). D. J.. 2012) Bibliography: Meure. Thermally mendable epoxy resin strengthened with carbon nanofibres. European Polymer Journal.. NAIRN. ZHANG. Confirmation of the healing mechanism in a mendable EMAA–epoxy resin. pp. T. MEURE. X.524-531..420-424. Wu. Effect of Carbon Nanofibers on Thermal Conductivity of Carbon Fiber Reinforced Composites In-text: (Liang. Confirmation of the healing mechanism in a mendable EMAA–epoxy resin In-text: (Meure et al. S. and Khor.. GESTOS.... 295(5). S. VARLEY. MAYO. Mayo. S.. WANG. M. C. J.. . 2013) Bibliography: Zhang. Wang.814-820. Y. S. Composites Part A: Applied Science and Manufacturing. AND ALTAN. R. WU.. AND WANG. 56. H. Gestos. C. 48(3). H. (2010). A.. X. S. A. pp. Thermally mendable epoxy resin strengthened with carbon nanofibres In-text: (Zhang et al. and Wang.. J. S... Procedia Engineering. pp. Nairn. Furman. Saha. K. LIANG. C. C. H. Varley.45-52..Bibliography: Meure. Effect of Carbon Nanofibers on Thermal Conductivity of Carbon Fiber Reinforced Composites. R.. SAHA. and Furman. 55. S. Macromolecular Materials and Engineering. 2013) Bibliography: Liang. M. pp. M. S. Lin... S. Saha and Altan. Poly[ethylene-co-(methacrylic acid)] Healing Agents for Mendable Carbon Fiber Laminates. LIN. K.

.. T. Santos. and Sundararaj.. M. RICHARDSON. SANTOS.2126-2142.. H. Review of the mechanical properties of carbon nanofiber/polymer composites. LIN. RICHARDSON.. J. The effect of carbon nanofibres on self-healing epoxy/poly(ε-caprolactone) blends In-text: (Zhang et t al. 2011) Bibliography: Al-Saleh. 94(12). M. J. AND SUNDARARAJ. P. P. M. (2012). J.. REIS. CHEUNG. M. Impact response of Kevlar composites with filled epoxy matrix In-text: (Reis et al. 72(15).. J. Review of the mechanical properties of carbon nanofiber/polymer composites In-text: (Al-Saleh and Sundararaj. . C. P. 2012) Bibliography: Zhang. Composites Science and Technology.. (2011). pp.. P. Lin.. P. AND SANTOS. 42(12).3520-3528. AND WANG.. (2012). J. J. J. J. C.. AND SANTOS. Composites Part A: Applied Science and Manufacturing. Cheung. FERREIRA. S. 2012) Bibliography REIS. Richardson. C. Impact response of Kevlar composites with filled epoxy matrix. P..1952-1959. SANTOS. pp. The effect of carbon nanofibres on self-healing epoxy/poly(ε-caprolactone) blends. T. H. Composite Structures. AL-SALEH.ZHANG. U. M. and Wang. Impact response of Kevlar composites with filled epoxy matrix In-text: (Reis et al. S.. pp. Ferreira. 2012) Bibliography: Reis.. FERREIRA.. U. and Santos.

Instron. AITM Airbus Test Method for determination of Compression Strength After Impact on Fibre Reinforced P . 2015] .COM AITM Airbus Test Method for determination of Compression Strength After Impact on Fibre Reinforced P .com/en-au/testing-solutions/by-test-type/impact/aitm-airbus-test-method? region=Australia [Accessed 29 Mar.com. 2015) Bibliography: Instron.INSTRON.instron. [online] Available at: http://www.Instron In-text: (Instron.com. (2015).