Nanosilica Modification of Elastomer-Modified 

VARTM Epoxy Resins for Improved Resin 

and Composite Toughness 

by Jason Robinette, Andres Bujanda, Daniel DeSchepper, Jessica Dibelka, 

Phillip Costanzo, Robert Jensen, and Steven McKnight 

ARL-TR-4084 April 2007 

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Army Research Laboratory 

Aberdeen Proving Ground, MD 21005-5069 

ARL-TR-4084 April 2007 

Nanosilica Modification of Elastomer-Modified 

VARTM Epoxy Resins for Improved Resin 

and Composite Toughness 

Jason Robinette, Andres Bujanda, Daniel DeSchepper, Jessica Dibelka, 

Phillip Costanzo, Robert Jensen, and Steven McKnight 

Weapons and Materials Research Directorate, ARL 

Approved for public release; distribution is unlimited. 
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Nanosilica Modification of Elastomer-Modified VARTM Epoxy Resins for 

Improved Resin and Composite Toughness 

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AH84 

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Jason Robinette, Andres Bujanda, Daniel DeSchepper, Jessica Dibelka, Phillip 

Costanzo, Robert Jensen, and Steven McKnight 

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14. ABSTRACT 

Recent publications have reported a synergy between rubber and silica in modified epoxy resins that results in significantly 

improved fracture toughness without reductions in other material properties. In this work, we seek to achieve the same type of

synergy in commercial vacuum-assisted resin transfer molding (VARTM) epoxy resins, SC15 and SC79, produced by Applied 

Polymeric, Inc. Nanopox F400 (Hanse Chemie) containing 40 weight-percent epoxy-functional silica in a diglycidyl bisphenolF (DGEBF) epoxy was blended with the VARTM resins to add various silica loadings in the systems. It was found that the 

presence of DGEBF influenced resin properties more than silica. This monomer impacted crosslink density and other material 

properties. The crosslink density of SC15 was increased and resulted in reductions in resin fracture toughness, mode II 

composite fracture toughness, and increased damage area in impact performance. The crosslink density of SC79 was reduced 

upon the addition of DGEBF contained in the Nanopox. At 10 weight-percent silica, resin fracture toughness, mode II 

composite toughness, and impact properties were improved due to decreased matrix crosslink density and the presence of silica. 

Finally, morphological studies showed that silica influences the rubber phase separation in a model epoxy system and VARTM 

epoxies. Further research will investigate the effects of epoxy-functional silica addition to phase separation mechanisms in 

rubber-toughened epoxies. 

15. SUBJECT TERMS

nanosilica, rubber toughening, VARTM, epoxy, mode II, end notch flexure 

16. SECURITY CLASSIFICATION OF: 

19a. NAME OF RESPONSIBLE PERSON

Jason Robinette 

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410-306-2100 

Standard Form 298 (Rev. 8/98) 

Prescribed by ANSI Std. Z39.18 
Contents 

List of Figures iv

List of Tables iv

Acknowledgments v

1. Introduction 1

2. Experimental 2

2.1 Materials and Resin Formulations...................................................................................2 

2.2 Resin Characterization ....................................................................................................3 

2.3 Composite Characterization ............................................................................................4 

2.4 Morphological Characterization......................................................................................7 

3. Results and Discussion 8

3.1 Resin Properties...............................................................................................................8 

3.2 Composite Properties ....................................................................................................10 

3.3 Comparisons Between Model and VARTM Epoxies...................................................13 

4. Conclusion 16

5. References 17

Distribution List 19 

iii
List of Figures 

Figure 1. Sample geometry of ENF specimens. .............................................................................4 

Figure 2. Alternative ESIS crack initiation criteria for ENF test methods (10). ............................5 

Figure 3. A plot of fracture toughness (G1c) as a function of silica concentration in SC15 and 

SC79 resins. A rules-of-mixture line is shown for each resin that accounts for the change 

in fracture toughness as a result of blending DGEBF into the formulation...............................9 

Figure 4. Digital images of the composite strike face after drop tower impact testing. 

Imaging software is used to calculate the damage area. Each panel image is 

100 × 100 mm. .........................................................................................................................12 

Figure 5. TEM images at a magnification of 60,000× for 10 weight-percent CTBN-modified 

DGEBF, SC15, and SC79 resins..............................................................................................14 

Figure 6. FESEM images of CTBN-modified DGEBF, SC15, and SC79 with 0 and 

10 weight-percent silica modification......................................................................................15 

List of Tables 

Table 1. SC-15 resin formulations..................................................................................................2 

Table 2. SC-79 resin formulations..................................................................................................2 

Table 3. SC-15 resin properties. .....................................................................................................8 

Table 4. SC-79 resin properties. .....................................................................................................9 

Table 5. End notch flexure (ENF) mode II properties..................................................................11 

Table 6. Drop tower impact properties. ........................................................................................11 

Table 7. Summary of short beam shear and flexural strengths.....................................................12 

Table 8. Tensile properties for 0 and 10 weight-percent silica-modified resin and composite....13 

Table 9. Fracture toughness comparisons between a model and VARTM epoxies. ....................14 

iv
Acknowledgments 

This research was also supported in part by an appointment to the research participation at the 

U.S. Army Research Laboratory (ARL) administered by the Oak Ridge Institute for Science and 

Education through an interagency agreement between the U.S. Department of Energy and ARL. 

v
INTENTIONALLY LEFT BLANK.

vi
1. Introduction 

Vacuum-assisted resin transfer molding (VARTM) is a low-cost, efficient method for processing 

fiber-reinforced composites. Thermosetting resins utilizing VARTM techniques are required to 

have a viscosity lower than 1000 cP and long working times. Furthermore, resins that cure at 

room temperature are of particular interest due to reduction of residual stresses in the final part, 

energy costs for curing, and effects of thermal expansion mismatches between the composite 

constituents. A major drawback with VARTM resins is low fracture energies. Many techniques 

have been used to increase the fracture toughness of these polymer systems. One of the most 

common toughening methods involves adding soluble rubber modifiers that phase separately into 

micron-sized particles during cure (1, 2). Fracture energies have been increased by an order of 

magnitude for amine-cured epoxy resins modified with acrylonitrile-butadiene rubber modifiers 

(3). Another method for improving toughness has been the addition of inorganic inclusions. Lee 

and Yee reported three-fold increases in fracture toughness of an amine-cured epoxy with 

approximately 25-μm glass particles (4). 

Recent work by Kinloch et al. (5) and Sprenger et al. (6, 7) has shown a synergistic toughening 

effect by adding rubber and inorganic nanosilica to a diglycidyl ether of bisphenol-F (DGEBF) 

epoxy cured with diethyltoluene diamine. The addition of each individual modifier mildly 

increases toughness. When 9 weight-percent carboxyl-terminated acrylonitrile-butadiene 

(CTBN) rubber is added to the system, the fracture toughness (critical strain energy release rate, 

G1C) increases from 100 to 410 J/m2

. The addition of 7.8 weight-percent of 20-nm epoxyfunctional silica increases G1C to 390 J/m2

. When a combination of CTBN and silica are added, 

resin fracture toughness was reported as high as 2000 J/m2. In this work, we seek to institute a 

synergistic toughening effect for rubber-modified SC15 and SC79 (Applied Polymeric) VARTM 

resins through the addition of a commercially available DGEBF-based resin containing 40 

weight-percent epoxy-functional silica (Nanopox F400). The effect of silica content on resin 

properties such as viscosity, glass transition temperature (Tg), and fracture toughness are studied. 

Glass-reinforced composites infused with SC15 and SC79 resins containing 0 and 10 weightpercent silica are evaluated with respect to mode II fracture, impact, short beam shear, tensile, 

and flexural properties. Finally, investigations of resin morphology are investigated using 

scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to elucidate 

differences in the VARTM resins and the model DGEBF systems. 

1
2. Experimental 

2.1 Materials and Resin Formulations 

SC15 and SC79 are commercial VARTM resins developed by Applied Polymeric Inc. (Benicia, 

CA). They are rubber-modified, epoxy-based resins that have low viscosity. Nanopox F400 

(Hanse Chemie, Geesthacht, Germany) is a commercial resin comprising 40 weight-percent 

silica and 60 weight-percent DGEBF (Epon 862). The silica particles have an average diameter 

of 20 nm and are chemically functionalized with epoxy groups. The epoxy equivalent weight 

(EEW) of the aforementioned materials is 173, 162, 171, and 295 g per equivalence for SC15, 

SC79, Epon 862, and Nanopox, respectively. The resin formulations studied in the work are 

given in tables 1 and 2. All systems were cured at 60 oC for 2 hr and 177 °C for 6 hr. 

Table 1. SC-15 resin formulations. 

Weight Fraction 

Silica Content 

(weight-percent) 

DGEBF Content

(weight-percent) 

EEW 

(g/equiv.) 

SC-15 

Part A 

SC-15 

Part B 

Nanopox 

F 400 

0 0 173.0 0.769 0.231 0.000 

1 1.50 177.0 0.746 0.229 0.025 

2.5 3.78 182.8 0.712 0.226 0.063 

5 7.50 192.5 0.656 0.219 0.125 

7.5 11.28 202.0 0.602 0.211 0.188 

10 15.00 211.2 0.549 0.201 0.250 

15 22.50 228.6 0.448 0.177 0.375 

Table 2. SC-79 resin formulations. 

Weight Fraction 

Silica Content 

(weight-percent) 

DGEBF Content

(weight-percent) 

EEW 

(g/equiv.) 

SC-79 

Part A 

SC-79 

Part B 

Nanopox 

F 400 

0 0 162.0 0.714 0.286 0.000 

1 1.50 166.6 0.691 0.284 0.025 

2.5 3.78 173.6 0.656 0.281 0.063 

5 7.50 184.9 0.601 0.274 0.125 

7.5 11.28 195.9 0.548 0.265 0.188 

10 15.00 206.5 0.497 0.253 0.250 

15 22.50 226.3 0.401 0.224 0.375 

Additional materials were purchased to compare SC15 and SC79 to the model epoxy system 

developed by Kinloch et al. (5) and Sprenger et al. (6, 7). Epon 862 and diethyltoluene diamine 

(Epicure W) were purchased from Resolution Performance Products (Houston, TX). CTBN 

(Noveon, Cleveland, OH) was used as the model rubber modifier. 

2
2.2 Resin Characterization 

Three-point, single-edge notch bend (SENB) specimens were used for fracture toughness 

measurements. ASTM D 5045-93 (8) specifies that the sample dimensions of 50 × 12.5 

× 6.25 mm3

 to assure plain strain conditions. An initial crack was made by creating a notch in 

the specimens a distance that was half the sample thickness. A sharp razor blade was used to 

initiate a crack at the base of the notches. Approximately 10 samples were tested for each resin 

system. The samples were tested using an Instron 4505 equipped with a three-point bend fixture, 

a 1-kN load cell, and tested at a crosshead speed of 10 mm/min. All tests were performed at 

ambient conditions. When tests were completed, the fracture surfaces of all specimens were 

examined for signs of plastic deformation. If plastic deformation was apparent, the sample was 

not included in the reported results. The critical-stress-intensity factor (K1C) and critical strain 

energy release rate (G1C) at a span (S) to width (W) ratio of 4 are defined by the following 

expressions: 

2 2

1

1

(1 ) C

C

K G

E

−ν = ,

 (1) 

where 

,

 (2) 1/ 2

1 ( ) K PBW f C = ( ) x

and 

2

1/2

3/2

1.99 (1 )(2.15 3.93 2.7 () 6 (1 2 )(1 )x x x

fx x

x x

⎡ −− − + x ⎤ ⎣ ⎦ = + −

,

 (3) 

and 

P = load, 

B = sample thickness, 

W = sample width, 

a = crack length, 

x = 0.45 < a/W < 0.55, 

E = modulus, assumed 2.0 GPa for SC15 and SC79, and 

ν = Poisson’s ratio, assumed 0.35 for SC15 and SC79. 

A TA Instruments dynamic mechanical analyzer (DMA), DMA Q800, with a 20-mm dual 

cantilever clamp frame was used to evaluate the storage modulus, E', and Tg of each resin 

system. Temperature scans with an oscillation frequency of 1 Hz were performed at a rate of 

2 °C/min starting from –20 to 160 °C for SC15 and to 230 °C for SC79. The Tg was taken as the 

peak of the loss modulus, E", curve. Resin viscosity was measured using an AR2000 rheometer. 

All viscosities were reported at a constant shear rate of 300 s-1. 

3
2.3 Composite Characterization

S2 glass-reinforced composite panels with approximate dimensions of 90 × 60 × 5 mm3 were 

fabricated using the VARTM process (9). The woven fabric was stacked using 0°–90° fabric 

lay-ups. The S2 glass consisted of nominal 24 oz/yd2

 plain-woven 5 × 5, 250-yield roving with 

463 sizing (the roving was made by Advanced Glassfiber Yarns and woven by Knytex – product 

SBA240F). SC15 and SC79 resins with 0 and 10 weight-percent silica were fabricated following 

the formulations and cure schedule outlined in section 2.1. Final volume fractions of glass fiber 

present in the composite panels were typically found to lie between 0.51 and 0.53 for all samples 

tested. Void content of the cured composite panels was not determined but was known to be 

consistently near 2% for this process (10). 

Mode II composite properties were measured using an end notched flexure (ENF) specimen. 

Typical sample dimensions are given in figure 1. The initial crack length was formed by adding 

a 0.0005-in-thick Teflon* spacer at the middle interlayer during composite fabrication. The 

crack length, a, was 50 mm, and L was chosen to be 100 mm so that the ratio of a/L was 0.5. 

Sample width, b, and thickness, h, were 20 and 2.5 mm, respectively. Samples were subjected to 

a three-point bend at a crosshead speed of 2.5 mm/min. 

Figure 1. Sample geometry of ENF specimens. 

The compliance method, given as τmax, was used to determine the mode II strain energy release 

rate, GIIC. In reality, the relationship between compliance, C, and crack length, a, was much 

more complicated for the ENF test than for mode I measurements. Although many equations 

have been proposed, the following equation accounting for modulus based on classic beam 

theory has been most widely used: 

max

max

3

4

P

bt

τ = ,

 (4) 

and 

3 3

3

2 3 , 8L a

Cbh

+ Ε =′ (5) 

 *

Teflon is a registered trademark of E.I. duPont de Nemours and Company. 

4
where E' is the effective Young’s modulus and L is the half-span length. Therefore, the 

expression for GIIC is obtained for small values of (E'E/Gs) (h/a)

2

 , where Gs is the interlaminar 

shear modulus and is given by the following: 

2

3 3

9

2 (2 3 ) IIc

a P G

bL a

δ = +

. (6) 

Several criteria have been developed by the European Structural Integrity Society (ESIS) to 

establish crack initiation. Figure 2 shows a typical load-displacement curve for an ENF test. 

Crack initiation is defined as the point of deviation from initial slope linearity (NL), the point of 

intersection between a line with a 5% offset in initial slope and the load-displacement data (5% 

offset), or the maximum load value (Max). 

NL

5% offset 

Max load 

displacement

Figure 2. Alternative ESIS crack initiation criteria for ENF 

test methods (11). 

The impact properties of the composite panels were measured using a Dynatup Drop Weight 

System. Samples were cut into 100 × 100 × 5 mm3

 squares and impacted with a 12.7-mm 

diameter hemispherical impact striker. Experimentally measured values of impact energy 

(Eimpact), impact velocity (Vimpact), and maximum force (Pmax) were recorded from the instrument 

and are summarized in the results section. The impact energy absorbed to maximum force (Emax) 

and total energy absorbed (Etotal) were calculated using the instrument software (12). Deflection 

data were not recorded. To measure the projected postimpact damage area, a digital image was 

taken of each damaged panel on a light box, and a pixel area ratio of the projected damaged area 

to the undamaged area was analyzed using an image analysis software package (13). Actual 

projected damage area could then be determined by multiplying the actual sample dimensions by 

5
the computer-generated pixel ratio. Minimums of five samples were tested for each composite 

panel set. 

The short-beam shear strength (SH) of each composite system was tested following ASTM 

D 2344-84 (14). Five specimens were tested for each composite. Each specimen was subjected 

to a three-point bend using an Instron model 4505 equipped with a 4.45-kN load cell and a 

crosshead rate of 1.27 mm/min. The span (s)-to-depth (d) ratio was approximately 4:1. The 

short-beam shear strength was calculated using the following equation, where P is the measured 

force at failure: 

4bd

P3 S B

H = .

 (7) 

Flexural strength was measured with 80- × 12.5- × 5-mm composite panel samples using the 

ASTM D 790 (15) testing method. The test was carried out in the three-point bending mode 

configuration. Testing was completed with the span length (L)-to-width (b) ratio set to the 

standard 16:1 using a minimum of five samples for each composite formulation. An Instron 

model 4505 equipped with a 4.45-kN load cell was used at a cross-head rate of 1.27 mm/min. 

The equation used to calculate flexural modulus (Eflex) is given next, where the slope of the 

tangent (m) is found by drawing a tangent to the steepest initial straight-line portion of the loaddeflection curve. Breaking force (P) was taken from force vs. displacement data, and the 

maximum fiber stress (σmax) was calculated using the following equations. 

3

3

H

bd4

mL E = , 

(8) 

and 

2

3 , 2 maxPL

bd

σ =

 (9)

where d is the depth of the specimen. 

Tensile properties for the SC-15 and SC-79 epoxies and composites were evaluated according to 

ASTM D 3039 (16). An Instron 1125 universal testing frame was used to gather load data and 

failure stress values. A 5-kN load cell was used for the SC-79 and SC-15 epoxy specimens, and 

a 100-kN load cell was used for the composite systems. Strain data was obtained for the 

specimens utilizing a video image correlation (VIC) system. Testing was conducted in 

displacement control, with displacement rates adjusted so the engineering strain rate was 0.001/s 

for each specimen size (~6.0 mm/min). Two valid tests were conducted for each material and 

composite system. 

The VIC system is a noncontact strain measurement method in which two cameras are used to 

capture video of the specimen during the deformation process. By first introducing a “speckle” 

6
pattern of black and white dots on the gage portion of the specimen, it is possible to track the 

deformation of the sample by tracking the movement of the pattern on the surface. This is 

accomplished in real time by simultaneously recording load data during video capture. After 

calibrating the camera orientation and position using a customized grid of dots and fiduciary 

circles, it is possible to calculate the displacement and strain of the specimen. The VIC is 

beneficial over conventional strain measurement techniques because it measures displacement 

directly off the specimen gage length, unlike a linear voltage displacement transducer or typical 

strain gage that first convert global displacement into electrical signal. Additionally, once 

displacement data is correlated for a specimen, it is relatively facile to evaluate a more plenary 

set of mechanical properties for the material. These include, but are not limited to, elastic 

modulus, shear modulus, and Poisson’s ratio. The VIC system used for the SC-15 and SC-79 

epoxies and composites was a hardware and software package developed by Correlated Solutions 

Incorporated. Mono 12-bit Retiga OEM cameras fitted with Micro Nikkor 105-mm lenses were 

used for video capture. Video and load data were recorded using VicSnap software version 

3.0D, and analysis was carried out on Vic-3D software version 2006 0.0. The ultimate tensile 

strength (Ftu), Young’s modulus (E), and Poisson’s ratio (ν) were calculated using the following 

equations: 

bd

P Ftu = , (10) 

Δε

σΔ E = , (11) 

and 

allongitudin

lateral

εΔ

Δε

ν = .

 (12)

2.4 Morphological Characterization 

The rubber morphology for the various epoxy systems was evaluated with a field emission 

scanning electron microscope (FESEM), Hitachi model S4700, using an acceleration voltage 

ranging between 3 and 5 kV. All samples were gold sputtered prior to SEM evaluation. The 

surfaces inspected with the FESEM were obtained from the fracture surface of the specimens 

used in the SENB experiments. 

TEM was used to inspect the dispersion of silica in the epoxy matrices. A Leica Ultracut UCT 

microtome with a diamond knife was utilized to cut sections approximately 300 Å in thickness 

that were subsequently collected upon Formvar-coated TEM grids. TEM was completed using 

JEOL 200 CX instrument operated at a 120-kV accelerating voltage. 

7
3. Results and Discussion 

The purpose of this work was to translate a synergistic toughening effect between nanosilica and 

rubber modifiers from a model DGEBF system studied in literature (5–7) to commercial, 

elastomer-modified VARTM epoxy resin systems (SC15 and SC79). First, resin properties, such 

as fracture toughness, Tg, and viscosity, were evaluated with varying levels of silica content. 

Second, the most promising resin formulations were manufactured in glass-reinforced 

composites. The composite properties evaluated included mode II fracture toughness, impact, 

short beam shear (SBS), flexural, and tensile properties. Finally, TEM and FESEM techniques 

were used to compare the rubber and silica morphology of the model epoxy system to the 

VARTM resins. This analysis allowed for the formulation of hypotheses explaining the resin 

and composite properties. 

3.1 Resin Properties 

The rationale of silica addition is to improve fracture toughness of the rubber-modified VARTM 

resins without sacrificing other resin properties such as viscosity, Tg, and modulus. A summary 

of SC15 and SC79 properties with varying silica concentrations is given in tables 3 and 4, 

respectively. Figure 3 gives a plot of the fracture toughness as silica concentration increases. 

Since silica is premixed with a DGEBF monomer, increasing silica content also increases the 

amount of DGEBF in the system. In addition to the effects of silica on resin properties, DGEBF 

will also influence resin properties by changing the overall EEW of the epoxy monomers. To 

distinguish the effects of silica addition from DGEBF, the fracture toughness of DGEBF cured 

with stoichiometric amounts of respective curing agents was found. The fracture toughness of 

DGEBF cured with SC15 and SC79 amines was 700 ± 60 J/m2

 and 260 ± 30 J/m2, respectively. 

By using a rule-of-mixtures approach, the fracture toughness of SC epoxies and DGEBF could 

be predicted. These predictions are represented as dashed lines in figure 3. Any deviations from 

the dashed line can be assumed as the influence of the silica. 

Table 3. SC-15 resin properties. 

Silica Content 

(weight-percent) 

Viscosity 

(cP) 

Tg 

(°C) 

E' at 25 °C

(GPa) 

K1c

(MPa·m0.5) 

G1c

(J/m2

) 

0 280 94.1 2.37 1.70 ± 0.16 900 ± 170 

1 440 94.7 2.44 1.89 ± 0.11 1020 ± 110 

2.5 480 98.1 2.31 1.86 ± 0.21 720 ± 100 

5 460 99.8 2.49 1.67 ± 0.12 790 ± 140 

7.5 520 99.4 2.61 1.77 ± 0.16 790 ± 120 

10 580 97.3 2.37 1.73 ± 0.10 880 ± 70 

15 1130 93.1 2.96 1.74 ± 0.09 700 ± 100 

8
Table 4. SC-79 resin properties. 

Silica Content 

(weight-percent) 

Viscosity 

(cP) 

Tg 

(°C) 

E' at 25 °C

(GPa) 

K1c

(MPa·m0.5) 

G1c

(J/m2

) 

0 220 180.0 2.91 1.04 ± 0.29 180 ± 60 

1 250 179.4 2.84 0.70 ± 0.13 90 ± 40 

2.5 300 174.4 2.66 1.03 ± 0.41 240 ± 130 

5 370 174.0 2.83 0.93 ± 0.21 230 ± 100 

7.5 430 167.7 3.01 1.03 ± 0.39 200 ± 90 

10 490 165.3 3.35 1.06 ± 0.18 380 ± 50 

15 1090 162.3 2.91 1.27 ± 0.08 250 ± 60 

0

300

600

900

1200

0 510 15

Silica Concentration (wt.%)

Fracture Toughness, G1c (J/m2

)

SC15

SC79

Figure 3. A plot of fracture toughness (G1c) as a function of silica 

concentration in SC15 and SC79 resins. A rules-ofmixture line is shown for each resin that accounts for the 

change in fracture toughness as a result of blending 

DGEBF into the formulation. 

According to figure 3, the influence of DGEBF is more prominent than the presence of silica. 

For SC15, the DGEBF had a lower EEW than the epoxy part of the SC15. Therefore, the overall 

crosslink density of the matrix phase increased and caused the resin to become more brittle. 

Increasing silica content and thus the concentration of DGEBF inherently reduced the fracture 

toughness of the system. A most promising silica-modified formulation occurred at 10 weightpercent silica. The G1C of this formulation, 880 ± 70 J/m2

, was essentially equal to the baseline 

resin (900 ± 170 J/m2

). Composite properties using this formulation will be addressed in the 

subsequent section. 

9
The addition of Nanopox has the opposite effect on SC79. Since DGEBF had a higher EEW 

than the SC79 epoxy, the overall EEW of the system increased and matrix crosslink density 

decreased. At most silica concentrations shown in figure 3, the influence of silica appears to be 

minor. At 10 weight-percent silica, however, the combination of decreased crosslink density and 

the presence of silica yielded the highest fracture toughness. The G1C was improved from 

180 ± 60 J/m2

 for the unmodified SC79 to 380 ± 50 J/m2. This resin formulation will be used to 

evaluate composite properties in the next section. 

In addition to fracture toughness, resin properties such as viscosity and Tg are affected by 

Nanopox modification. The DGEBF contained in Nanopox has a higher viscosity than the SC15 

and SC79 epoxy parts. Therefore, as increasing silica content increases, the viscosity will 

increase due to the coupled DGEBF. Increased viscosity does not become a factor in VARTM 

processing until the viscosity is above 1000 cP. As shown in tables 3 and 4, all formulations 

with silica content of 10 weight-percent and lower would not create processing issues. However, 

15 weight-percent silica yielded viscosities over 1000 cP and cannot be utilized as VARTM 

resins. 

The fracture toughness results indicated a strong influence of DGEBF on the crosslink density. 

The matrix crosslink density also impacted the Tg in thermosetting polymers. For SC15, the Tg

was not strongly affected by the addition of Nanopox. The largest improvement in Tg occurred 

at 5 weight-percent silica, increasing from 94.1 to 99.8 °C. Further, Nanopox modification 

slightly decreased the Tg. The SC79 system showed a stronger influence of DGEBF on Tg. This 

property steadily decreased from 180 to 162.3 °C (15 weight-percent silica). 

3.2 Composite Properties 

The previous section demonstrated that 10 weight-percent silica had the highest toughness 

performance for both resin systems. Therefore, composites were made comprising 10 weightpercent silica and were compared to both baseline resin systems. ENF is an effective technique 

for comparing mode II fracture toughness in fiber-reinforced composites. Table 5 summarizes 

all of the results from the ENF tests. As was discussed in the experimental section, there are 

three points that can be used to define the point of crack propagation. These criteria 

(nonlinearity, 5% offset of initial slope, and maximum load) are presented. The trends are the 

same for each criterion, so we will focus on the 5% offset data in our discussion. For SC15, the 

addition of 10 weight-percent silica reduced GII from 1240 ± 80 J/m2

 to 990 ± 90 J/m2. The 

SC79 system showed the opposite trend, where silica addition improved GII from 590 ± 20 J/m2

to 720 ± 70 J/m2

. These results reinforced the trends shown in the resin systems. The 

combination of decreased matrix crosslink density and the addition of silica improved SC79 

resin and composite toughness. The increased crosslink density in SC15 detracted from any 

potential improvements provided by the silica. 

10
Table 5. End notch flexure (ENF) mode II properties. 

Resin Silica Content 

(weight-percent) 

Nonlinearity GII

(J/m2) 

5% Offset GII

(J/m2) 

Maximum Load GII

(J/m2

) 

SC-15 0 370 ± 40 1240 ± 80 3130 ± 370 

10 300 ± 30 990 ± 90 2840 ± 170 

SC-79 0 150 ± 30 590 ± 20 1580 ± 80 

10 210 ± 40 720 ± 70 2100 ± 400 

Drop tower experiments were carried out to correlate the resin and composite toughness to 

ultimate impact properties. Table 6 gives the tabulated results of these experiments. Each 

composite was impacted with approximately 103 J of energy. The total energy absorbed by the 

composite, Etotal, correlated to the amount of impact energy absorbed by the composite. 

Therefore, a tough composite would have a relatively low Etotal,, high impact load (Pmax), high 

energy absorbed at maximum load (Emax), and a minimal damage area. SC15 showed negligible 

difference in impact load and total energy absorbed. The most significant difference was the size 

of the damage area. The addition of Nanopox increased the damage area from 950 ± 80 mm2

 to 

1340 ± 130 mm2

, thus indicating a reduction in overall composite toughness and impact 

properties. Figure 4 shows the strike face of damaged panels for the SC15 and SC79 systems. 

Table 6. Drop tower impact properties. 

Resin Silica Content 

(weight-percent) 

Eimpact

(J) 

Pmax

(kN) 

Emax

(J) 

Etotal

(J) 

Damage Area 

(mm2

) 

SC15 0 103.0 ± 0.8 16.2 ± 0.2 88.5 ± 4.0 79.7 ± 2.2 950 ± 80 

10 103.3 ± 0.3 15.7 ± 0.5 87.7 ± 10.1 79.3 ± 5.4 1340 ± 130 

SC79 0 103.1 ± 0.3 15.7 ± 0.5 66.6 ± 2.2 89.6 ± 2.6 2280 ± 210 

10 102.7 ± 0.2 15.4 ± 0.5 67.3 ± 6.0 84.3 ± 2.0 2040 ± 150 

The impact properties of the SC79 systems were more sensitive to silica addition than the SC15 

resins. Although there was no difference in impact load, there were substantial differences in 

total energy absorbed and damage area. When silica was present in the resin, Etotal decreased 

from 89.6 ± 2.6 J to 84.3 ± 2.0 J and damage area reduced from 2280 ± 210 mm2 to 2040 

± 150 mm2

. The improvement in resin and composite toughness by adding Nanopox translated 

directly to impact properties. 

In addition to toughness and impact properties, structural properties (SBS, flexural, and tensile 

strengths) were also investigated, summarized in table 7. SBS properties were generally 

influenced by the interfacial performance of the fiber with the polymer matrix. The addition of 

silica had very little effect on these properties. SC15 showed a slight reduction from 47.8 

± 0.9 MPa to 44.4 ± 1.6 MPa. For SC79, a minor increase from 34.7 ± 5.4 MPa to 35.8 

± 1.1 MPa occurred. 

11
SC 15, 0 wt.% silica SC 15, 10 wt.% silica 

SC 79, 0 wt.% silica SC 79, 10 wt.% silica 

Figure 4. Digital images of the composite strike face after drop tower impact 

testing. Imaging software is used to calculate the damage area. Each 

panel image is 100 × 100 mm. 

Table 7. Summary of short beam shear and flexural strengths. 

SBS Flexural Tests 

Resin Silica Content 

(weight-percent)

SH

(MPa) 

σmax

(MPa) 

EH

(GPa) 

SC15 0 47.8 ± 0.9 404.3 ± 41.8 22.1 ± 0.9

10 44.4 ± 1.6 464.1 ± 24.2 24.4 ± 0.8

SC79 0 34.7 ± 5.4 441.0 ± 30.0 24.9 ± 1.6

10 35.8 ± 1.1 366.2 ± 13.8 25.1 ± 0.9

Table 7 indicates that the maximum fiber stress, σmax, is more sensitive to silica modification 

than modulus of elasticity, EH, with respect to flexural experiments. Upon silica addition, EH

slightly changed from 22.1 ± 0.9 MPa to 24.4 ± 0.8 MPa for SC15 and from 24.9 ± 1.6 MPa to 

25.1 ± 0.9 MPa for SC79. For σmax, SC15 substantially increased from 404.3 ± 41.8 MPa to 

464.1 ± 24.2 MPa, while a decrease from 441.0 ± 30.0 MPa to 366.2 ± 13.8 MPa was found for 

SC79. Again, these trends were more indicative of a change in crosslink density than to any 

silica addition. 

12
Resin and composite tensile properties, given in table 8, were measured for the SC15 and SC79 

systems. In general, a toughened resin or composite resulted in decreased structural properties. 

For SC15, resin and composite toughness decreased with the addition of silica, accompanied 

with an increase in tensile properties. These trends were more evident in the resin, where 

Young’s modulus (E) and ultimate tensile strength (Ftu) increased from 2.63 to 3.46 GPa and 

30.5 to 38.3 MPa, with the addition of 10 weight-percent silica, respectively. Although the 

composite structural properties were influenced more by the glass reinforcement than the resin, 

the SC15 composite data showed similar trends to the resin data. The E and Ftu increased from 

18.17 to 18.76 GPa and 320.6 to 487.9 MPa, with 10 weight-percent silica addition. As was also 

seen in the toughness data, adding silica had the opposite effect on SC79. The resin E and Ftu

decreased from 4.10 to 3.25 GPa and 27.7 to 16.5 MPa, respectively. The composite E and Ftu

decreased from 22.13 to 22.01 GPa and 419.5 to 380.1 MPa, respectively. 

Table 8. Tensile properties for 0 and 10 weight-percent silicamodified resin and composite. 

Resin Composite 

Resin Silica Content 

(weight-percent)

Ftu

(MPa)

E 

(GPa)

υ Ftu

(MPa)

E 

(GPa)

υ

SC15 0 30.5 2.63 0.38 320.6 18.17 NA 

10 38.3 3.46 0.38 487.9 18.76 NA 

SC79 0 27.7 4.10 0.41 419.5 22.13 0.19 

10 16.5 3.25 0.39 380.1 22.01 0.22 

Note: NA = not available. 

In general, resin properties directly translated to composite properties. The influence of DGEBF 

on the crosslink density of the matrix exceeded any toughening effects associated with silica. 

Since DGEBF had a lower EEW than the SC15 epoxy monomers, the matrix had a lower EEW 

and higher crosslink density. This corresponded to reduced fracture energies and impact 

properties. Adding DGEBF to the SC79 resin system decreased the matrix crosslink density. 

This, combined with the presence of silica, resulted in mild improvements in toughness and 

impact properties. In addition to changing crosslink density, adding Nanopox reduced the 

overall rubber content. This may be another explanation for a lack of synergistic toughening in 

the VARTM resins. Finally, the presence of DGEBF and nanosilica may potentially influence 

the phase separation of the rubber during cure. The next section will address any morphological 

changes. 

3.3 Comparisons Between Model and VARTM Epoxies 

According to resin and composite properties, synergistic toughening between an elastomer and 

nanosilica in epoxy did not translate from model epoxy systems to the VARTM epoxy resins. 

This section will identify differences between these systems that could be potential explanations 

for this behavior. The model epoxy system contained the same DGEBF found in Nanopox 

(Epon 862). Therefore, adding a rubber modifier, CTBN, ensured that the concentration of all 

13
components in these systems was known. SC15 and SC79 are proprietary resins in which the 

type and concentration of elastomer are unknown. Table 9 compares the fracture toughness 

(G1C) of a model 10 weight-percent CTBN-modified DGEBF system to the VARTM resins. 

This comparison further illustrated that the VARTM resins did not achieve a synergy between 

the rubber and silica. The model DGEBF resin was improved almost five-fold from the best 

VARTM resin (SC79, 10 weight-percent silica), whereas the best VARTM resin improvement 

was 111.1% for SC79. 

Table 9. Fracture toughness comparisons between a model and VARTM 

epoxies. 

G1C [=] J/m2

10 Weight-Percent 

CTBN-Modified DGEBF SC15 SC79 

0 weight-percent silica 390 ± 70 900 ± 170 180 ± 60 

10 weight-percent silica 1890 ± 190 880 ± 70 380 ± 50 

Difference +474.9% –2.2% +111.1% 

One theory for a potential toughening mechanism in these systems is the phase in which the 

silica assembles. Figure 5 gives TEM images that are used to distinguish the rubber and silica in 

these systems. Comparing these systems, it was clear that the silica migrated into the epoxy 

phase during rubber phase separation. Therefore, silica assembly had a negligible influence with 

respect to the toughening effect in these systems. Future work will focus on ways of controlling 

silica migration to further disprove its importance as a toughening mechanism. 

1 micron 

1 micron 1 micron 

CTBN-modified 

SC15 SC79

Figure 5. TEM images at a magnification of 60,000× for 10 weight-percent CTBNmodified DGEBF, SC15, and SC79 resins. 

14
FESEM images were taken to compare the difference in rubber morphology for the various resin 

systems, given in figure 6. One noticeable observation for the CTBN-modified DGEBF system 

was the size and dispersion of the phase-separated rubber particles. The system without silica 

had larger particles more sparsely dispersed throughout the matrix. When 10 weight-percent 

silica was added to the system, the number of particles increased, the particle size decreased, and 

the particles were more closely dispersed. A likely explanation was that the silica forced more 

nucleation sites for the rubber particles. The dispersion of the rubber could be a potential factor 

in toughening. Future work will focus on studying factors about the model DGEBF system that 

make it suitable for synergy between rubber and silica modifiers. We will investigate methods of 

controlling rubber phase morphology to determine whether the way in which silica influences 

phase separation is the predominant toughening mechanism. 

CTBNmodified 

DGEBF 

SC15 

SC79 

0 wt. % silica 10 wt. % silica 

Figure 6. FESEM images of CTBN-modified DGEBF, SC15, and SC79 with 0 and 10 

weight-percent silica modification. 

15
4. Conclusion 

The goal of this work was to achieve an enhanced fracture toughness of commercial VARTM 

epoxy resins (SC15 and SC79) through a synergy between nanosilica particles and elastomer 

modifiers. Nanopox is a commercial DGEBF resin containing 40 weight-percent nanosilica 

particles. By blending the VARTM resins with various amounts of Nanopox, we were able to 

investigate the effect of silica concentration of resin properties, such as fracture toughness, 

viscosity, and Tg. The presence of DGEBF in the Nanopox impacted matrix crosslink density, 

increasing for SC15 and decreasing for SC79. It was found that changing crosslink density was 

as influential in toughening as adding silica. Generally, SC15 experienced decreased toughening 

effects while SC79 showed slight increases in fracture toughness. Furthermore, SC79 containing 

10 weight-percent silica increased fracture toughness from 180 ± 60 J/m2

 to 380 ± 50 J/m2 and 

proved to be the most promising formulation. Glass-reinforced composite properties followed 

the same trends found for the resin properties. The SC15 composite showed that silica 

modification reduced mode II fracture toughness and impact properties due to decreased resin 

toughness. On the other hand, SC79 had improved mode II fracture toughness and impact 

properties. TEM and FESEM analysis showed that silica changed the dispersion and size of the 

rubber morphology in these systems. For a model DGEBF system, rubber morphology was more 

significantly affected by silica than for the VARTM epoxies. Future work will further elucidate 

the effect of silica on rubber phase separation and potentially explain the reason that VARTM 

resins did not achieve a toughening synergy. 

16
5. References 

1. Collyer, A., Ed. Rubber Toughened Engineering Plastics; Chapman and Hall: London, 

1994. 

2. Riew, C., Ed. Rubber Toughened Plastics; American Chemical Society: Washington, 1989. 

3. Pearson, R. A.; Yee, A. F. Toughening Mechanisms in Elastomer-Modified Epoxies. J. 

Mater. Sci. 1989, 24, 2571–2580. 

4. Lee, J.; Yee, A. F. Role of Inherent Matrix Toughness on Fracture of Glass Bead Filled 

Epoxies. Polymer 2000, 41, 8375–8385. 

5. Kinloch, A. J.; Lee, J. H.; Taylor, A. C.; Sprenger, S.; Eger, C. Toughening Structural 

Adhesives via Nano- and Micro-Phase Inclusions. J. of Adhesion 2003, 79, 867–873. 

6. Sprenger, S.; Kinloch, A. J.; Taylor, A. C.; Mohammed, R. D.; Eger, C. Rubber-Toughened 

FRCs Optimized by Nanoparticles. JEC Composites 2005, 9, 73–76. 

7. Sprenger, S.; Kinloch, A. J.; Taylor, A. C.; Mohammed, R. D.; Eger, C. Rubber-Toughened 

GFRCs Optimized by Nanoparticles. JEC Composites 2005, 12, 66–69. 

8. ASTM D 5045-93. Standard Test Methods for Plane-Strain Fracture Toughness and Strain 

Energy Release Rate of Plastic Materials. Designation D 5045-99; American Society for 

Testing and Materials 1999. 

9. Hsiao, K. T.; Gillespie, J. W.; Advani, S. G.; Fink, B. K. Role of Vacuum Pressure and Port 

Locations on Flow Front Control for Liquid Composite Molding Processes. Polymer 

Composites 2001, 22, 660. 

10. Ghiorse, S. R. U.S. Army Research Laboratory, Aberdeen Proving Ground, MD. Private 

communication, 15 August 2005. 

11. De Morais, A. B.; Silva, J. F.; Marques, A. T.; De Castro, P. T. Mode II Interlaminar 

Fracture of Filament Wound Angle-Ply Specimens. Appl. Comp. Mater. 2002, 9, 117–129. 

12. Instron Dynatup 930-1 (version 1.21) software. 

13. Rasband, W. Image J (version 1.30). National Institutes of Health, Bethesda, MD, 2003. 

14. ASTM D 2344-84. Standard Test Methods for Apparent Interlaminar Shear Strength of 

Parallel Fiber Composites by Short-Beam Method. Designation D 2344-84; American 

Society for Testing and Materials 1995. 

17
15. ASTM D 790. Standard Test Methods for Flexural Properties of Unreinforced and 

Reinforced Plastics and Electrical Insulating Materials. Designation D 790-96a; American 

Society for Testing and Materials 2003. 

16. ASTM D 3039. Standard Test Methods for Tensile Properties of Polymer Matrix Composite 

Materials. Designation D 3039/D 3039M-95a; American Society for Testing and Materials 

2006. 

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