CNT PULLOUT MODEL APPLICATION

Input material data acquisition

The fracture toughening model described in Section 5.4 requires several types of material input data. For CNT and CNF fillers, the most difficult issue is related to the variability of physical (e.g. diameter, length, multiple walls etc.) and mechanical properties (e.g. tensile strength, elastic modulus), that sometimes are properly described in the form of a statistical distribution. Moreover, some changes of the initial system (e.g. volume fraction, CNT length etc.) can be induced during functionalization, dispersion processes, manufacturing processes. In the following paragraphs the acquisition of CNT/CNF material input data is illustrated, based on vendor datasheets,

a) b)

c) d)

Figure 5.79: SEM images of mode I fracture surfaces [91]: a) composite with a long GPS-CNT epoxy interlayer; b) long GPS-GPS-CNTs in the interlayer: cavities in circles were possibly created by CNT pull-out; c) composite with a GPS-CNF interlayer; d) GPS-CNFs with epoxy layers bonded to the CNF surface.

178

experimental measurements, and literature data. The experimental cases are divided into cases 1-2 and cases 3-4 for material properties concerning CNFs and CNTs, respectively.

CNF material properties

CNFs used in cases 1-2 were supplied by Applied Sciences Inc. (Cedarville, OH) in the form of Vapor-Grown Carbon NanoFibers (CNFs).

a) b) c)

PR-24-XT Production Full scale

Diameter,

nanometers 60 to 150 Length,

nanometers 30,000 to 100,000

Comments As grown material essentially free of CVD carbon

Figure 5.80: CNF details: a) 3D rendering; b) longitudinal section; c) TEM image and material characteristics - (from Applied Sciences Inc. (Cedarville, OH) http://apsci.com/?page_id=19).

Three grades of VGNCFs (with the commercial name Pyrograf-III) are available by Applied Sciences: (I) as-grown VGCNFs subjected to post-fabrication pyrolytic stripping to remove polyaromatic hydrocarbon residues (commercially designated as PR-24-XT-PS), (II) high temperature heat treated VGCNFs with smooth surfaces HHT-LD), and (III) surface functionalized VGCNFs (PR-24-XT-HHT-LD-OX) produced by subjecting the high temperature heat treated fibers to an oxidative treatment in a wet chemical process that changes the surface oxygen and nitrogen contents and promotes bonded interactions with organic matrices. PR-24-XT-HHT-LD CNFs were used to manufacture multiscale reinforced composites.

Concerning the mechanical properties of PR-24-XT-HHT-LD CNFs, Ozkan et al. [98] measured the mechanical strength and the elastic modulus of individual nanofibers of pyrolytically stripped, high temperature heat-treated and oxidized VGCNF by a MEMS (MicroelectromechanicalSystems tool) nanomechanical property characterization method. In another experimental work, Ozkan et al. [99] conducted nanoscale pull-out experiments in order to obtain the Interfacial Shear Strength (ISS) of individual VGCNF embedded in Epon 828™ difunctional bisphenol A/epichlorohydrin compounded with EPIKURE™ 3140 polyamide curing agent.

It is well known that dispersion processes reduce the length of nanotubes/nanofibers, as described in Section 5.2.1. For this reason, it is very important to know the CNF length distribution after sonication. From Zhu’s work [91]

the measurements of length distribution after different bath sonication time were reported. The CNF-filled resin mixtures were sonicated in an ultrasonic bath operating at 45 W and 38.5 kHz for 4 and 2 hours for CNFs and GPS functionalized CNFs, respectively (before the placement of the interlayer).The results of 4 hours bath sonication were considered as length distribution input data for both CNFs and GPS-CNFs cases. It should be noticed that in that case, the mass fraction of GPS-CNFs was equal to 0.05% wt whereas a weight percentage of 0.5% wt was used in the CNF reinforced interlayer for the reinforced composites Figure 5.81 reports experimental data (a) and fitted curves (b), according to the length distribution of equation 5.28. The resulting CNF average length was 3.7 µm, almost one order of magnitude less than the minimum initial value of CNF length according to the manufacturer.

Figure 5.81: UF-CNF length distribution after 1 and 4 hours of bath sonication dispersion

180 CNT material properties

CNTs used in cases 3-4 are were short hydroxyl-functionalized CNTs (OH-CNTs) and un-functionalized vertical grown CNTs (VG(OH-CNTs), both supplied by Cheaptubes (Brattleboro, VT). VGCNTs grown aligned to each other in the length direction with minimal entanglement. The information reported in Figure 5.82 have been gathered from the datasheet of the vendor.

Outer Diameter: 10-20nm Inside Diameter: 3-5nm Ash: <1.5 wt%

Purity: >95 wt%

Length: 0.5-2.0 m

Specific Surface Area: 233 m²/g Electrical

Conductivity: >100 S/cm Bulk density: 0.22 g/cm³ True density: ~2.1 g/cm³

Figure 5.82: Short OH Functionalized material properties and Short OH TEM image;

provided by http://www.cheaptubesinc.com/shortohcnts.htm#ixzz2HkbOislo Outer Diameter: 8-15nm

MWNTs Inside Diameter: 3-5nm Ash: <1.5 wt%

Purity: >95 wt%

Length: 10-50 m

Specific Surface Area: 233 m²/g Electrical Conductivity: >100 S/cm

Bulk density: 0.15 g/cm³ True density: ~2.1 g/cm³

Figure 5.83: VGCNTs material properties and VGCNTs TEM image; provided by http://www.cheaptubesinc.com/shortohcnts.htm#ixzz2HkbOislo

Concerning the mechanical properties of OH-CNTs and VGCNTs, the values reported in Table 5.5 were implemented in the model, on the basis of the available experimental values.

Table 5.10: Mechanical properties of CNTs used within the present study

Reinforcement Diameter (nm)

Young’s Modulus (GPa)

Tensile Strength (GPa)

Failure strain (%)

MWCNT [10, 11] 10–40 800 20–50 2–12

SWNT [100] 0.6–3 1000 10–52 5–10

With regard to length distribution of CNTs, the CNT-filled resin mixtures (short GPS-CNT epoxy and long GPS-CNT epoxy) were sonicated in an ultrasonic bath operating at 45 W and 38.5 kHz for 8 hours at 60°C. Actually no length distribution data were available from Zhu’s work [91]. However, in case of long GPS-CNT epoxy, it is assumed in the current investigation that the residual length distribution after sonication roughly corresponds to the length distribution reported in [96] where residual lengths of a-MWCNTs (the same VGCNTs as in Zhu’s work) after 5 minutes of sonication in the mixture of epoxide and acetone were measured with the aim of predicting the modulus of MWCNT/epoxy composites. The weight fraction of a-MWCNTs in epoxide/acetone mixture was equivalent to 0.5 wt% in resin. The resulting average length was 0.77µm, almost one order of magnitude less than the initial value of VGCNT length (Figure 5.84).

Figure 5.84: Probability density distribution of a-MWCNTs (i.e. VGCNTs) after 5 minutes

182 Volume Fraction of CNFs/CNTs

The CNF/CNT volume fraction of, i.e. V_CNF, V_CNTs was calculated according to the rule of mixture:

( )

where W_f, is the CNF/CNT mass fraction and _f and _m are the CNF/CNT and matrix density, respectively. However, this value may be affected by uncertainty. For example, fracture toughness specimens were fabricated starting from 356 by 305 mm impregnated sheets and consolidated in a press at room temperature. When the resin rich interlayer was placed, a calculated amount of nanofilled resin, equivalent to the weight of resin in two plies of cured composite plate, was added to the surfaces of both sheets facing the midplane to serve as a nanofilled interlayer region on the fracture plane. This amount was estimate as ~14 grams. By considering the following values:

{

Obviously, a reasonable amount of interlayer material was “lost” during the manufacturing process (for instance 2 grams). The “expected” thickness of the nanofilled resin interlayer would be:

( )[ ( )]

( ) ( )

[ ] [ ]

However, since SEM observations revealed that the interlayer corresponded approximately to the space between glass fiber bundles (i.e. 0-20 μm), it is plausible that the epoxy in the interlayer was mostly bled out and the fillers were entrapped by glass fibers, leading to concentrated nanofillers at the fracture plane. This hypothesis is particularly true in case of CNFs, whose lengths (after sonication) are in the range of