Large thermoplastic composite

wind turbine blades

J. Teuwen (TU-Delft)

(We@Sea project 2004-012)

REPORT PhD@Sea
Large thermoplastic composite wind turbine blades
Process optimization for vacuum infusion of large blades

Julie Teuwen
December 2009

Outline
List of Figures .................................................................................................................................. iii
List of tables......................................................................................................................................v
1
Introduction ............................................................................................................................. 1
2
Thin laminates: process optimization...................................................................................... 3
2.1
Introduction..................................................................................................................... 3
2.2
Experimental .................................................................................................................. 3
2.3
Pot life ............................................................................................................................ 6
2.4
Infusion strategy ............................................................................................................. 7
2.5
Upscaling...................................................................................................................... 16
2.6
Cure.............................................................................................................................. 18
2.7
Post processing of APA-6 composites ......................................................................... 19
2.8
Conclusions .................................................................................................................. 23
3
Thick laminates: Heating methods........................................................................................ 25
3.1
Introduction................................................................................................................... 25
3.2
Experimental ................................................................................................................ 25
3.3
Heat distribution ........................................................................................................... 28
3.4
Comparison of heating methods .................................................................................. 34
3.5
Conclusions .................................................................................................................. 35
4
Reduction of cure shrinkage induced voids .......................................................................... 36
4.1
Introduction................................................................................................................... 36
4.2
Experimental ................................................................................................................ 36
4.3
Resin constitution ......................................................................................................... 38
4.4
Pure resin ..................................................................................................................... 39
4.5
Laminates ..................................................................................................................... 41
4.6
Conclusions .................................................................................................................. 42
5
Optimisation of fibre-to-matrix bond...................................................................................... 43
5.1
Introduction................................................................................................................... 43
5.2
Experimental ................................................................................................................ 43
5.3
Effect of fibre sizing ...................................................................................................... 44
5.4
Characterisation of glass rovings ................................................................................. 44
5.5
Vacuum infusion set-up for UD laminates.................................................................... 45
5.6
Characterisation of the UD-laminates .......................................................................... 47
5.7
Conclusions .................................................................................................................. 48
6
Conclusions and recommendations...................................................................................... 49
6.1
Conclusions .................................................................................................................. 49
6.2
Recommendations ....................................................................................................... 50
References .................................................................................................................................... 52

ii

List of Figures
Figure 1. Anionic polymerisation of caprolactam into polyamide-6 ................................................. 1
Figure 2. Aminosilane sized E-glass fibres...................................................................................... 3
Figure 3. Vacuum infusion set-up (from left to right: Mini Mixing Unit, buffer vessel, laminate and
heating device, resin trap and vacuum pump). ............................................................................... 4
Figure 4. Infrared panel as heating device for the laminate. ........................................................... 4
Figure 5. Viscosity in time of a reactive mixture with an initial buffer vessel residence temperature
(110 or 130C) and time (0, 5 or 13.5 min) ...................................................................................... 6
Figure 6. Degree of crystallinity of the inlet and the outlet of a vacuum-infused APA-6 composite 7
Figure 7. Temperature logging of the infusion (t=0sec) and reaction of a laminate at 160C at
three locations: resin inlet, middle and resin outlet ......................................................................... 7
Figure 8. De-blocking of carbamoylcaprolactam (step 1) and the subsequent formation of fibre-tomatrix bond (step 2)......................................................................................................................... 8
Figure 9. C-Scan images of APA-6 laminates at different infusion temperatures (120-150C) with
the inlet at the bottom side of the picture ........................................................................................ 9
Figure 10. Degree of conversion at different infusion temperatures ............................................. 10
Figure 11. Average short-beam strength values at different infusion temperatures ..................... 11
Figure 12. The effect of the degassing procedure on the inter laminar shear strength (ILSS) of the
composites..................................................................................................................................... 13
Figure 13. Flow front position during infusion and their corresponding flow rate at different inlet
tube cross-sections and infusion pressures. ................................................................................. 14
Figure 14. C-scan results for different infusion pressures - post-fill pressures respectively, with an
2
inlet tube cross-section of 20mm .................................................................................................. 14
Figure 15. Degree of conversion near the inlet and outlet of the laminates at different inlet tube
2
cross-sections [mm ] - infusion pressures [mbar] - cure pressures [mbar] ................................... 15
Figure 16. C-scan results for infusion temperature of 110C when inlet is not clamped during
heating (test 2)............................................................................................................................... 17
Figure 17. C-scan results for infusion temperature of 130C when inlet is not clamped during
heating (test 3)............................................................................................................................... 17
Figure 18. C-scan results for inlet clamping after infusion (test 4) ................................................ 17
Figure 19. Evolution of degree of crystallinity of pure resin in time............................................... 18
Figure 20. Evolution of degree of conversion of pure resin in time. .............................................. 18
Figure 21. Degree of crystallinity for different cure times .............................................................. 19
Figure 22. Short-beam strength for different cure times................................................................ 19
Figure 23. Change in crystallinity at different annealing temperatures (averaging the results for
different annealing times and cooling rates at the different annealing temperatures). ................. 21
Figure 24. Change in crystallinity at different annealing times (averaging the results for different
annealing temperatures and cooling rates at the different annealing times)................................. 21
Figure 25. Cooling rates at different annealing temperatures. ...................................................... 22
Figure 26. Change in crystallinity for different cooling rates.......................................................... 22
Figure 27. Short-beam strength for different annealing temperatures. ......................................... 22
Figure 28. Short-beam strength for different annealing time s...................................................... 22
Figure 29. Vacuum infusion bag for thick laminates with the coarse fabric weave....................... 26
Figure 30. (Kapton) Thermofoil Heater ................................................................................... 26
Figure 31. Position of the resistive mesh in the middle of the fabric lay-up and its connection to
the power supply............................................................................................................................ 27
Figure 32. Connection of the carbon fabric via two copper plate to the copper wire of the power
supply ............................................................................................................................................ 27
Figure 33. Position of the thermocouples through the thickness of the lay-up. ............................ 27
Figure 34.Glass beaker with cover lid and supporting plate ......................................................... 28
Figure 35.Viscosity measurements at different mould temperatures ............................................ 28
Figure 36. Adiabatic temperature measurements with an initial pot life of 5 minutes at 115C,
cured at different temperatures ..................................................................................................... 29
Figure 37. Heating profiles through the thickness of the laminate during heating from 110 to
180C with the heated platen......................................................................................................... 29

iii

Figure 38. Heating profiles of different mould plates using the infrared panels as heating device30
Figure 39. Heating profiles through the thickness of the laminate during heating from 110 to
180C with the infrared panels....................................................................................................... 30
Figure 40. Heating profiles through the thickness of the laminate during heating from 110 to
180C with a thermofoil on the mould side and an infrared panel at the top................................. 31
Figure 41. Comparison of heating profiles of laminates heated by double infrared, or by thermofoil
in combination with the top infrared panel. .................................................................................... 31
Figure 42. Cross-section of a cured 24 mm thick laminate heated by thermofoil in combination
with the top infrared panel. ............................................................................................................ 32
Figure 43. Heating profiles through the thickness of the laminate during heating from 110 to
180C with a resistive mesh in the middle of the fibre lay-up and the infrared heating as surface
heating ........................................................................................................................................... 32
Figure 44. Cross-section of laminates heated by a metal mesh or a carbon fabric in combination
with the intrared panels ................................................................................................................. 32
Figure 45. Heating profiles through the thickness of the laminate during heating from 110 to
180C with a resistive carbon fabric in the middle of the fibre lay-up and the infrared heating as
surface heating .............................................................................................................................. 33
Figure 46. Heating profiles of the heat input layers in the carbon fabric experiment. ................... 33
Figure 47. Heating distribution through the thickness in the carbon fabric experiment. ............... 33
Figure 48. Heating profiles through the thickness of the laminate during heating from 110 to
180C with a resistive carbon fabric in the middle of the fibre lay-up and the infrared heating as
surface heating .............................................................................................................................. 34
Figure 49. Heat distribution for different heating methods, before start of the chemical reaction. 35
Figure 50. Reactivity of the resin with different amounts of rubber. T1 stands for the infusion
window, T2 for the start of the polymerisation and T3 for the start of the crystallisation. The
system has been compared to the reaction times of the normal system. ..................................... 38
Figure 51. Viscosity versus time for different material systems: C-M and R-M at different testing
temperatures: 160-170 and 180C ................................................................................................ 38
Figure 52. Viscosity versus time for different material systems: R-M at7% and 20%wt and C-M. at
a testing temperature of 160C...................................................................................................... 39
Figure 53. Degree of crystallinity for the normal C-M system and for different amounts of rubber in
the R-M system.............................................................................................................................. 40
Figure 54. Enthalpy of cold crystallisation for the normal C-M system and for different amounts of
rubber in the R-M system. ............................................................................................................. 40
Figure 55. Peak temperature of cold crystallisation for the normal C-M system and for different
amounts of rubber in the R-M system. .......................................................................................... 40
Figure 56. E-modulus for the normal C-M system and for different amounts of rubber in the R-M
system. .......................................................................................................................................... 41
Figure 57. Dry impact resistance for the normal C-M system and for different amounts of rubber in
the R-M system.............................................................................................................................. 41
Figure 58. Dry and conditioned impact resistance for the normal C-M system and for different
amounts of rubber in the R-M system. .......................................................................................... 41
Figure 59. The impact resistance for specimens cured at 30 or 45 min, in dry or conditioned state,
for 7 and 10% of rubber in the R-M system................................................................................... 41
Figure 60. The degree of conversion for laminates with 15%wt rubber at different processing
temperatures.................................................................................................................................. 42
Figure 61. The degree of conversion for laminates manufactured at 180C, with different amounts
of rubber. ....................................................................................................................................... 42
Figure 62. The degree of crystallinity for laminates with 15%wt rubber........................................ 42
Figure 63. The degree of crystallinity for laminates manufactured at 180C, with different amounts
of rubber. ....................................................................................................................................... 42
Figure 64. Effect of the fibre sizing of the short-beam strength at different processing
temperatures.................................................................................................................................. 44
Figure 65. Comparison of the tensile strength of different fibre types........................................... 44
Figure 66. Al supporting plate (for both winding and infusion) ...................................................... 45
Figure 67. Dry filament wound fibres around Al supporting plate ................................................. 45

iv

Figure 68. Tacky-tape applied and in- and outlet connected to the mould set-up ........................ 46
Figure 69. Al covering plates placed on the fibres for better surface quality................................. 46
Figure 70. Fully vacuum bagged mould ready for infusion............................................................ 46
Figure 71. A fully cured UD laminate............................................................................................. 46
Figure 72. Average maximum transverse tensile strength of UD laminates for different infusion
parameters..................................................................................................................................... 48
Figure 73. Average maximum transverse tensile strength of .the upper and lower part of the
obtained UD laminate after infusion .............................................................................................. 48

List of tables
Table 1. Test matrix for the effect of the residence time and temperature on the viscosity of the
reactive resin in a buffer vessel ....................................................................................................... 6
Table 2. Physical properties at different infusion temperatures .................................................... 11
Table 3. The effect of the degassing procedure on the composite properties. ............................. 13
Table 4. Thickness (t) and inter laminar shear strength (ILSS) near the inlet and outlet of the
composites, and the infusion times at different infusion and post-fill pressures. .......................... 14
Table 5. Infusion settings for the infusion of long laminates.......................................................... 16
Table 6. Infusion times for the infusion of long laminates ............................................................. 17
Table 7. Comparison of heating rate of different heating methods ............................................... 34
Table 8. Infusion window for different material systems: C-M and R-M at different amount of R at
different testing temperatures........................................................................................................ 39
Table 9. Comparison of tensile properties of glass fibre rovings .................................................. 45
Table 10. Infusion parameters for the UD infusion process, for different type of tests ................. 46

1 Introduction
Nowadays, the development of production processes for large composite structures is of great
importance, especially for wind energy companies and their production of wind turbine blades
with lengths exceeding 60 meters. The life expectancy of 20 years of the wind turbine blades,
combined with the fact that wind energy is one of the fastest growing and most promising energy
source on the renewable energy market, also leads to the necessity of the development of a
recyclable material for the wind turbine blades.
Since thermoplastic composites can be fully recyclable and may lead to lower production times
compared to their thermoset composite counterparts, increased interest is shown in the
development of these composites. Other advantages of thermoplastic composites are the easy
assembly of parts through welding and their high toughness.
Thermoplastic composite materials are traditionally manufactured through melt processing using
a hot press or an autoclave. The melt processing technique however limits the size and thickness
of the obtainable parts. From the requirement of making large blades, the use of a different
process is needed. For thermoset large size wind turbine blades, a vacuum infusion process is
currently used. The vacuum infusion process uses a pressure difference between resin inlet and
resin outlet, as a driving force for infusing the resin into the dry fibre preform. The vacuum
infusion process has an atmospheric inlet pressure (p 1 bar) and an outlet pressure lower than
1 bar. Because the vacuum infusion process is a closed process (on one side a mould is present
and the other one a vacuum bag is used to seal the whole set-up), there are low volatile
emissions. The low weight combined with the low volatile emissions and low production costs
compared to other fabrications processes, makes the vacuum infusion process a valuable
alternative fabrication process technique for manufacturing of large composite structures [1].
However, several limitations for liquid moulding of thermoplastics can be observed: (i) a high
resin viscosity which impairs the wet-out of the reinforcement; (ii) the high temperature
processing requirement and (iii) a small processing window [2, 3]. The vacuum infusion process
can only be used with thermoplastic resins, when their poor impregnation characteristics can be
overcome by lowering the viscosity of the resin. The viscosity of thermoplastic resins is typically
100- 1000 Pa.s whereas infusion can only take place at a viscosity of 1 Pa.s or less.
A trade-off between the possible thermoplastic resins based on availability, costs and suitability
for the production process, resulted in the selection of anionic polyamide-6 (APA-6) as the most
suitable candidate, as shown in the work of K. van Rijswijk [4,p.35]. Due to the low viscosity at the
beginning of the reaction, followed by a fast reaction rate and the high conversion that can be
obtained, anionic polyamide-6 is very suitable for the vacuum infusion process. This report is
based on the research work that continued after van Rijswijks thesis on the PhD@Sea project.
O

C
N

NH

N
+

C
N

NH
C

O
N

NH
C

C
+

O
C

NH

C
N

O
NH

NH
C

C
+

O
C

C
N

NH

NH
C

O
n

Figure 1. Anionic polymerisation of caprolactam into polyamide-6

The reactive processing used combines all the manufacturing stages into one single production
step: after vacuum infusion of the reactive mixture into the fibre pre-form, a delayed in-situ
polymerisation of the monomer to the high molecular weight thermoplastic resin takes place. The
high molecular weight APA-6 is obtained through ring-opening polymerisation, as shown in Figure
1. When demoulding the composite, one hour after infusion, the cured, fully recyclable
thermoplastic composite part is obtained.

In the above-mentioned previous work, the resin constitution needed for the production of glass
fibre reinforced APA-6 composites was established and the most important parameters in the
process were identified. It was shown that APA-6 composites have the potential to be used for
wind turbine applications. The requirements, which can be set for the vacuum infusion of large,
thermoplastic wind turbine blades, are:
The manufacturing process must be able to produce homogeneous large composite parts.
The composite needs to be uniform in mechanical and resin properties, both in the flow
and through-the-thickness directions.
The manufacturing process needs to be suitable for production of complex parts, with
complex shapes and thickness variations.
The two previous requirements have to be met in combination with good mechanical
properties (static and dynamic) and optimum durability.
The previous research also posed a number of questions to be solved before these requirements
can be met with the APA-6 system:
Fluctuations in the composite properties were observed, both in the flow and through-thethickness directions, and also between laminates manufactured following the same
infusion strategy. A different infusion strategy and different heating methods will be tested
to overcome these problems.
For the optimization of the dynamic properties and the durability of the composite, the
fibre-to-matrix adhesion was identified as the most critical parameter. The effect of the
process parameters, as well as the effect of different fibre sizings, on the optimization of
the fibre-to-matrix bond needs to be investigated.
The research carried out up till now was focused on small laminates (with a length of 25
cm). More research is needed on bigger panels to investigate the effect of the flow length
on the properties of the laminates
Voids generated during the infusion and curing process have a detrimental effect on the
mechanical properties. Two different lines of research will be described in this report to
reduce the void content in the APA-6 composites: a further investigation on the infusion
strategy as well as a reduction in cure shrinkage by altering the resin constitution.
Chapter 2 of this report presents the optimization of the process for thin laminates. This
optimization is based on a number of factors: temperature, pot life, infusion strategy, up-scaling,
curing and post-processing. In Chapter 3, different heating methods and their potential for heating
thick-walled large composites are discussed. A different resin constitution is investigated to
minimize the voids and shrinkage of the composites and the results shown in Chapter 4. Finally,
the optimization of the fibre-to-matrix bond by testing different fibre sizings is presented in
Chapter 5. In Chapter 6, the conclusions and recommendations will be given.

2 Thin laminates: process optimization

2.1 Introduction
The previous work of van Rijswijk et al. [4] showed that the processing temperature is the most
important parameter in the infusion of APA-6 composites. The processing temperature results
from the sum of the external heat (heating device) and the internal heat (exothermic reaction of
the resin). As the effect of the temperature is thought to be significant for every stage in the
infusion process, all the steps will be investigated separately. Likewise, other relevant parameters
within every stage will be evaluated resulting in the following scheme:
1. Investigation of the effect of the pot life (time and temperature) on the reaction/reactivity
of the resin and the increment of its viscosity
2. Investigation of the impact of different infusion strategies, characterized by time,
temperature, pressure and velocity during infusion, on the homogeneity of the composite
3. Investigation of increased flow lengths
4. Investigation of the effect of post-curing or post-processing (different times and
temperatures)

2.2 Experimental
2.2.1 Materials
Resin material
For the vacuum infusion of the anionic polyamide-6 thermoplastic laminates, a reactive resin
mixture is used, which consists of three components: monomer, activator and initiator. The
anionic polymerisation grade -caprolactam monomer (APCaprolactam) was supplied by
Brggemann Chemicals, Germany. As the monomer is extremely sensitive to moisture, it was
stored at room temperature in PE sealed tanks with bags of silica gel..
The combination of the activator and the initiator and the specific doses relative to the monomer
content were researched and determined by van Rijswijk et al. [5]. The reaction of this
activator/initiator combination is slow initially, which provides a low viscous resin mixture at the
beginning of the reaction and guarantees sufficient time for the full wet-out of the fibre preform.
Two different activators were used for the studies in this section, activator C and activator T. They
were both used in a 1.2% mol concentration in combination with 1.2% mol of the initiator M. Both
the activator and the initiator were supplied by Brggemann Chemicals, Germany and were
stored under a nitrogen atmosphere in sealed aluminium lined polyethylene bags.
Glass fibres
E-glass fibre mats were used to reinforce the APA-6 composites. The 8-harness satin weave E2
glass fabrics (SS 0303 050, weave style 7781, 300 gram/m ) were supplied by Ten Cate
Advanced Composites bv., Nijverdal, The Netherlands. The chemical structure of the aminosilane
sized glass fibres is presented in Figure 2.

Figure 2. Aminosilane sized E-glass fibres

2.2.2 Processing methods

Preparation of the resin mixture
A special designed lab-scale mixing unit (Mini Mixing Unit 'MMU-TUDelft', Bronk Industrial b.v.,
The Netherlands), see Figure 3, is used to prepare, under a nitrogen atmosphere and at a
temperature of 110C, the resin mixture for infusion. After dispensing the volume needed for the
infusion of a laminate into a buffer vessel, the resin is degassed for 5 minutes to remove any N2

dissolved in the mixture during its storage in the MMU tanks. This buffer vessel is inserted in a
specially designed aluminium cylinder, which is placed on a heated plate to keep the vessel and
resin mixture at a temperature of 110C during infusion. For the research described in sections
2.3 and 2.4.2, the buffer vessel was also set at a temperature of 130C.

Figure 3. Vacuum infusion set-up (from left to right: Mini Mixing

Unit, buffer vessel, laminate and heating device, resin trap and
vacuum pump).

Figure 4. Infrared panel as heating device for the

laminate.

Production of test tubes

Glass test tubes with a diameter of 20 mm and a length of 150 mm (Schott-Fiolax) were used to
manufacture pure resin samples. The test tubes were preheated and flushed with nitrogen before
being filled with 50 ml of resin. They were then sealed to prevent moisture uptake and placed in
an insulated oil bath at 180C. After the cure cycle, they were quenched in water at room
temperature.
Infusion strategy 1
2
A balanced, symmetric 12-ply laminate (25x29cm ) is prepared for vacuum infusion and is placed
in the heating device for the production of the laminates, either in between a hot platen press or
two infrared panels. The dry fibre preform is then heated to the chosen processing temperature,
which is also the cure temperature; a temperature between 150C and 190C. After degassing,
the resin is allowed to flow through the inlet injection line into the laminate. The resin injection and
fibre compaction are achieved under a vacuum of 250 mbar. When the resin reaches the outlet,
the resin inlet tube is closed and the part is ready to be cured at the chosen cure temperature.
The vacuum is maintained during the cure cycle of one hour.
Infusion strategy 2
2
A balanced, symmetric 12-ply laminate (25x29cm ) is prepared for vacuum infusion and is placed
between two infrared panels, which is the heating device used, as it can be seen in Figure 4.
Prior to infusion, the dry fibre preform is heated to the same temperature as the buffer vessel and
the MMU, ensuring an isothermal infusion. After degassing, the resin is allowed to flow through
the inlet injection line into the laminate. The resin injection and fibre compaction are achieved
under a vacuum of 3 or 250 mbar. When the resin reaches the line-injection outlet, the resin inlet
tube is closed and the infused laminate is heated to the required processing temperature of
180C. The vacuum is maintained during the cure cyc le of one hour.

2.2.3 Analysis methods

Viscosity measurements
The viscosity of the resin was measured by means of a concentric cylinder viscometer Bohlin V88
(speed 6, spindle type 6). A special mould was designed to measure the viscosity versus time of
the reactive resin.

Degree of conversion
To determine the degree of conversion (DOC) of the polymer, samples of the composite plate
were taken at 5 cm from the resin inlet and outlet. After drying the samples at 50C in a vacuum
oven for at least 48 hours, they were weighed (mtot) and refluxed overnight in demineralised water.
After this process, the residue was dried and weighed again. As the monomer dissolves in the
water, the mass loss can be attributed to the monomer (mmon). Additionally, the weight of the
fibres (mfib) was determined by burning off these residues in a carbolite oven at 565C for one
hour; according to ASTM D 258402. The degree of conversion can then be calculated as follows:

m mon
DOC = 1
m tot m fib

100 %

(1)

It should be taken into account that low molecular oligomers susceptible to be formed during
polymerisation also dissolve during the reflux process [6]. As these oligomers, as well as the
monomer, do not have any load carrying capabilities, Eq. 1 quantifies the amount of non-load
carrying substances in the composite but does not provide the exact degree of conversion.
Degree of crystallinity
The degree of crystallinity (Xc) and the melting temperature (Tm) of the polymer were determined
by means of a Perkin Elmer Differential Scanning Calorimeter (DSC). Disc-shaped samples of
approximately 5 mg (msp) were taken from the laminate at the same location as the degree of
conversion samples and were dried at 50C in a vacuum oven for at least 48 hours. In the DSC,
the test sample was held at 25C for two minutes an d then heated up to 240C at a rate of 10C
per minute. The results had to be corrected in account of the fibre content of the sample (mfib),
that was determined by burning off the resin after the DSC test. The degree of crystallinity was
calculated as follows:

Xc =

m sp
H m
1

H100 m sp m fib DOC

100%

(2)

100

In which Hm is the melting enthalpy of the specimen [J/g] and H100 is the melting enthalpy of a
fully crystalline polyamide-6 (H100= 190 J/g) [7]. The third term in Eq. 2 is a correction factor for
the degree of conversion of the sample.
Ultrasonic inspection
To check the homogeneity of the laminate, a high frequency (10 MHz) ultrasonic C-scan was
used. A single through-transmission mode was used to analyse differences in quality within the
material, with water as the contact medium. Scans were performed at a speed of 352 mm/s to
obtain images with a grid length of 0.5 mm and a width of 1 mm that were analyzed using ALIS
software.
Short-beam strength
The short-beam strength tests were conducted on a Zwick Roell 20 KN testing machine
according to the ASTM D2344 standard. The test specimens for the short-beam strength test
3
were rectangular shaped and with the following nominal dimensions: 16.2 x 5.4 x 2.7 mm . From
the maximum force (Pmax), the interlaminar shear strength (ILSS) was be calculated as follows:

ILSS = 0.75

Pmax
b t

(3)

In which b and t are the width and thickness of the specimen, respectively. A minimum of 5
specimens per condition was tested. According to the reference standard, the short-beam
strength test is suited for comparative testing of composite materials, provided that failures occur
consistently, i.e. in the same mode.
Temperature measurements
Both the polymerisation and crystallization process involve an exothermal reaction [8]. To
observe the temperature behaviour of the laminate during infusion and cure, a temperature

logging test was carried out. Three type K thermocouples were positioned at several locations
between the layers 6 and 7 of the glass fabric laminate.

2.3 Pot life

The effect of the residence time and the temperature of the reactive resin in the buffer vessel
(before infusion) on the resin properties and the resin viscosity were investigated. The viscosity
measurements were done according to the test method described above. The mould used for the
viscosity measurements was set at a curing temperature of 180C. The temperature of the buffer
vessel and the residence time of the reactive resin inside were varied within the test according to
the test matrix in Table 1. The viscosity versus time of a mixture poured into the viscosity mould
immediately after mixing was used as a baseline for this experiment. The time limit of 13.5 min
was set by the requirement that the resin needs to be pourable into the viscosity mould after the
preset residence time in the buffer vessel. At the critical buffer vessel temperature of 130C, this
requirement was met at approximately 13.5 min.
Table 1. Test matrix for the effect of the residence time and temperature on the viscosity of the reactive resin in a buffer
vessel

Temperature of buffer vessel [C]/

Residence time [min]
110C
130C
No buffer vessel (baseline)

0
min

5 min

13.5 min

X
X

X
X

From the test results, it could be concluded that the longer the residence time, the higher the
initial viscosity, especially significant for higher temperatures in the buffer vessel as it can be seen
in Figure 5. For the long residence time and the buffer vessel temperature of 130C it was seen
that the initial viscosity does not drop to the baseline viscosity after heating up the resin to the
mould temperature, showing that a reaction already took place during the residence time in this
vessel. For this testing condition, it was also seen that the sharp increase in viscosity until 1 Pa.s
(which is the viscosity limit for vacuum infusion of composites) occurs earlier than in the baseline,
thus reducing the infusion time.
1,1
1
*-0

0,9

110-5

Viscosity [Pa.s]

0,8

110-13.5

0,7

130-5.5
130-13.5

0,6
0,5
0,4
0,3
0,2
0,1
0
-0,1
0

Time [min]

Figure 5. Viscosity in time of a reactive mixture with an initial buffer vessel residence temperature (110 or 130C) and time
(0, 5 or 13.5 min)

Therefore, it can be concluded that the longer the residence time and the higher the initial buffer
vessel temperature, the higher the initial viscosity and the faster the reaction. Since the infusion
of large products, like large wind turbine blades, requires long residence times, a deeper insight
in the effect of this critical parameter is needed to find optimal infusion strategies that do not
compromise the resin properties. It is believed that a deeper knowledge on the reaction kinetics
of the resin will help understanding the reaction and the effect of the residence time and the
temperature. With this purpose, initial tests were performed and the definition of the semiempirical equations for the simulation of the resin reaction has been recently started.

2.4 Infusion strategy

Some research was focused on the infusion strategy pursuing ways to increase the homogeneity
of the composites. Firstly, different infusion strategies were investigated (see 2.2.2), as in the
work of van Rijswijk et al. And secondly, the research was focused on the effect of the different
infusion parameters (temperature, time, pressure) on the laminate properties and its homogeneity.

2.4.1 Optimization of infusion temperature for APA-6 composites

While manufacturing glass fibre reinforced anionic polyamide-6 composites, it was observed that
the usual high temperature vacuum infusion process (infusion strategy 1, in section 2.2.2)
induces thermal and chemical gradients in the flow direction. A change in the production process
was tested to try and solve this problem: both the resin and the dry fibre pre-form were kept at the
same temperature during infusion, after which they were heated to the required curing
temperature. In this investigation, initiator M and activator T were used. The effect of the infusion
temperature was investigated and it was ascertained that at all temperatures a certain gradient
was present, although it was less pronounced with a lower injection temperature. However, the
mechanical properties did not necessarily give the best results at these low infusion temperatures
due to an increased heating time to the required curing temperature. It is thought that the heating
rate is of high importance for the polymerisation reaction. If the heating rate is too low, the
polymerisation reaction will start at a low temperature, while the crystallisation reaction occurs
simultaneously [4]. Therefore the reactive groups will get trapped inside a crystal and the
polymerisation reaction will be hindered. Therefore, a trade-off had to be made between the
reduction in gradient at low infusion temperatures and the heating time to the cure temperature.
Temperature gradient
As mentioned before, the current infusion strategy for the production of the laminates induces a
gradient of properties in the flow direction. During the impregnation of the laminate, the resin from
the buffer vessel is at a temperature of 110C, whe reas the fibre bed itself is at the required
processing/curing temperature, which ranges from 150-190C, see infusion strategy 1, section
2.2.2.
When infused, the resin at the outlet is at a higher temperature than at the inlet, since it must
pass through the fibre bed, which is at the processing temperature. Due to this temperature
gradient in the flow direction, a difference in properties between the inlet and the outlet is
expected. To get an overview of these differences, the degree of conversion and crystallinity were
measured for several processing temperatures. Likewise, the temperature was measured by
placing themocouples at several locations within the laminate.
175
60

165

50

Temperature [C]

Degree of crystallinity [%]

170
55

45
40
35
30

160
155
150
145

Tmould = 160C (inlet)

Tmould = 160C (center)
Tmould = 160C (outlet)

APA-6 composite (sized/inlet)

25

140

APA-6 composite (sized/outlet)

20

135
140

150

160

170

180

190

200

M ould temperature [C]

Figure 6. Degree of crystallinity of the inlet and the outlet of a

vacuum-infused APA-6 composite

10

15

20

25

Time [min]

Figure 7. Temperature logging of the infusion (t=0sec) and

reaction of a laminate at 160C at three locations: resin inlet, middle
and resin outlet

The lower temperature at the inlet is translated into a higher crystallinity of the resin in that part of
the laminate, as it can be observed in Figure 6. This can be explained taking into account that the
thermodynamic driving force to crystallize is higher for decreasing temperatures [6]. Therefore,
the rate of crystal growth and, as a result, the degree of crystallinity, is higher at the inlet.
It should be noted that the results in this section on the temperature gradient were obtained with a
different activator, namely activator C in the resin mixture. The degree of crystallinity results for
the laminates in which the activator T, initiator M was used, show the same behaviour as the
results in Figure 6.
Because of the higher temperatures at the resin outlet, the polymerisation as well as the
crystallisation process starts at the outlet of the laminate. The reaction will then move towards the
inlet opposite to the flow direction, as it can be seen in Figure 7, in which the peaks represent the
polymerisation exothermal reaction. This also induces a gradient in the composite properties as
well as the occurrence of voids near the inlet of the composite, which is explained in more detail
in ref. 15.
Depletion of activator in flow direction
The same temperature gradient in the direction of the flow was observed when investigating the T
activator. Previous research on APA-6 mainly focused on the initiator M and activator C
combination for the reactive resin mixture [4-5, 10-11]. Both activators are blocked isocyanates
which can unblock above their de-blocking temperature [12]. This is an equilibrium chemical
reaction, as shown in Figure 8, step 1. Activator T has a lower unblocking temperature (125C)
compared to activator C, which de-blocks at a temperature of 160C. When the activator is in the
unblocked state, it has the ability to form branches in a similar way as in the neat resin [10]. It can
also chemically react with the aminosilane sizing on the glass fibres by the formation of urea links,
as it can be seen in Figure 8, step 2. The difunctional nature of the activator causes the polymer
chains to grow from the fibre surface, while still having one side of the chemical group that is able
to polymerise, as can seen in Figure 1. These chains can then form an interpenetrating network
with the polymer chains in the bulk matrix, enhancing the fibre-to-matrix bond significantly.
Due to the presence of unblocked activators, it was shown that the M-T resin system has better
bonding properties. It is however thought that activator T already attaches to the fibres during
infusion, leading to a depletion of the activator concentration in the flow direction and creating a
difference in the resin constitution between the inlet and the outlet. The difference between the
inlet and outlet properties was more present in the non-isothermal infusion when activator T was
used.

Figure 8. De-blocking of carbamoylcaprolactam (step 1) and the subsequent formation of fibre-to-matrix

bond (step 2)

Optimization of the infusion temperature

To eliminate the temperature gradient and the filtering effect of the activator through the laminate,
the following change in the processing procedure was investigated: The dry fibre pre-form was
not heated to the required processing temperature prior to infusion but to the same (lower)
temperature as the resin in the buffer vessel. As a result, the temperature gradient was eliminated
in the production process. The lower infusion temperature also leads to less unblocked activators,
and thus a lower filtering of the activator is expected. After infusion, the laminate was heated to
the required processing temperature of 180C. In th is part of the study, activator T was used.
The quality of the glass-fibre reinforced APA-6 composites not only depends on the chemical
composition of the resin but also on the processing temperature. In previous research on the neat
APA-6 resin by van Rijswijk et al. [10], it was shown that the polymerisation temperature is the
most important parameter for the resin properties.
If the infusion temperature is below the de-blocking temperature of the activator, but above the
initiation temperature for the polymerisation, the blocked activators will take part in the
polymerisation reaction, as shown in Figure 1. Hence, when the temperature rises above the deblocking temperature, during the heating phase of the production process, less activator groups
will be available for the de-blocking reaction, resulting in a lower fibre-to-matrix bond.
However, when the infusion temperature is above the de-blocking temperature of the activator, it
can be in an unblocked state during infusion and hence react with the fibres during infusion,
leading to the previously observed filtering (see section on filtering of the chemical ingredients).
To investigate the effect of the infusion temperature, glass fibre reinforced APA-6 composites
were infused at temperatures between 110 and 150C with an interval of 10C. They were then
heated to a cure temperature of 180C, with a heati ng rate of 16C/min. For every infusion
temperature, two or more laminates were produced and tested. The properties of the resulting
composites were investigated by means of a non-destructive C-scan test (overview of the
composites quality), a degree of conversion test and degree of crystallinity test (assessment of
the resin properties in the flow direction) and a short-beam strength test (mechanical properties).
Results
C-scan

120C

130C

140C

150C

Figure 9. C-Scan images of APA-6 laminates at different infusion temperatures (120-150C) with the inlet at the bottom
side of the picture

As it can be seen in the C-scan pictures in Figure 9, there is a transition in the damping of the
ultrasonic signal in the flow direction at all infusion temperatures. It can therefore be concluded
that filtering is still taking place, resulting in a change in the composite quality between the inlet
and outlet areas of the laminate. In the vacuum infusion process, three spacers were used to be
able to control the fibre compaction and infusion rate, one at the inlet of the laminate and two
near the outlet. Their influence on the resin flow during infusion is clearly visible and hence the
transition is not as uniform as expected.

The best quality was found at the inlet areas of the laminates manufactured with infusion
temperatures of 130 and 140C. The C-scan results f or the infusion temperatures of 120 and
150C are similar to each other, although the lower quality of the laminates has to be addressed
differently for both cases, as explained in the paragraph on the optimisation of the infusion
temperature. The result of 120C is thought to be c aused by the long heating time required to
reach the cure temperature, whereas at 150C the lo w quality can be ascribed to a high filtering
of the activator and therefore a less reactive resin system. For all the infusion temperatures, it is
expected that voids arise when a low reaction rate has been established.
Physical properties of the composites
The results for the degree of conversion are shown in Figure 10. As it can be seen in this graph,
there is a difference between the inlet and outlet areas of the laminate at all infusion
temperatures. Since the quality of the laminates decreases severely towards the outlet, the
degree of conversion at that area shows a bigger scatter. For the results of the inlet, however,
there is a parabolic trend with a clear optimum, as indicated in the graph. A maximum is found at
130C, which is believed to indicate an optimum equ ilibrium between the blocked and unblocked
state of the activator.
99

97

DOC [%]

95

93

91

inlet
panel 1
inlet
panel 2
inlet
panel 3
outlet
panel 1
outlet
panel 2
outlet
panel 3

89

87

85
100

110

120

130

140

150

160

Temperature [C]

Figure 10. Degree of conversion at different infusion temperatures

At infusion temperatures lower than 130C, the equi librium for the activator is mostly at the
blocked side during the infusion, thus promoting polymer growth. The heating rate to the required
curing temperature is not sufficiently high to shift the de-blocking equilibrium to the unblocked
side (Figure 8, step 1) before the first initiator anions react with the activator, see Figure 1. This
eliminates the possibility of linking to the aminosilane sizing groups on the fibre surface, creating
a poor fibre-to-matrix bond, as it will be shown when discussing the mechanical properties (see
Figure 11). As almost no activator is depleted, a too high activator concentration will be present in
the bulk matrix, thus resulting in extensive oligomer formation [10], which causes the degree of
conversion to drop as explained in section 2.2.3. For infusion temperatures above 130C, more
filtering of the activator will take place. Therefore resulting in a lower reaction rate and hence a
lower degree of conversion. For all the infusion temperatures considered in this research,
however, an enhancement of the polymer growth compared to the non-isothermal infusion was
observed (see Table 2).
The difference between the inlet and outlet is also present in the degree of crystallinity (see Table
2), with a higher crystallinity at the inlet area of the laminate. Research on the interface of APA-6
composites showed that a good fibre-to-matrix bond resulted in a lower degree of crystallinity
[13]. However, it will be shown that does not correspond with a poor fibre-to-matrix bond
compared with the outlet properties, as will be shown in the next paragraph. The degree of
crystallinity at the inlet found for the isothermal infusion was higher than for the non-isothermal
infusion process.

10

Table 2. Physical properties at different infusion temperatures

Infusion
temperature [C]
110C
120C
130C
140C
150C
Nonisothermal
infusion

Degree
of
crystallinity [%]
inlet
outlet
34
31
33
29
34
30
31
28
34
29

31

29

Degree
of
conversion [%]
inlet
outlet
92
94
94
93
95
95
94
92
93
93

92

92

Mechanical properties
The results for the short-beam strength are shown in Figure 11. The difference between the inlet
and outlet areas of the laminate, as seen in the C-scan results, is visible in the mechanical
properties as well, except for the infusion temperature of 110 C. At this temperature, the filtering
of the activator throughout the laminate is expected to be at its lowest level, as it is represented in
the mechanical behaviour of the composites. The mechanical properties at this temperature are
however low compared to other infusion temperatures, due to a poor fibre-to-matrix bond.
90
outlet

inlet

Short-beam strength [MPa]

80

70

60

50

40

30
100

110

120

130

140

150

160

Infusion temperature [C]

Figure 11. Average short-beam strength values at different infusion temperatures

In general, the mechanical properties at the inlet are higher than at the outlet, which is related to
the higher degree of crystallinity at the inlet. The mechanical properties of the laminates are
however not only dependent on the physical properties of the resin but also on the ability to
create a fibre-to-matrix bond. The best mechanical properties are found at an infusion
temperature of 130C. It can therefore be concluded that at that temperature an optimum
equilibrium is found between the unblocked state of the activator, which provides the good fibreto-matrix bond, and its blocked state, which ensures a good polymerisation for the current heating
rate of 16C/min. With the non-isothermal infusion process, the difference in mechanical
properties in the flow direction was around 25%. With the isothermal infusion at the optimal
temperature of 130C a difference of 15% was observed, confirming a lower filtering throughout
the laminate, while still maintaining good physical properties. If the heating rate of the composites
could be increased, this optimum might be found at a lower infusion temperature, with even lower
filtering as a result.
Conclusions
To overcome thermal and chemical composition gradients, a new infusion strategy was proposed
for the high temperature vacuum infusion process of glass fibre reinforced APA-6 composites:
Both the resin and the dry fibre pre-form were at the same temperature during infusion after
which the infused preform was heated to the required curing temperature. Research was done on

11

the infusion temperature to study its effect on the composite properties and their homogeneity in
the flow direction. Some filtering could be observed at all the infusion temperatures, which could
be mainly attributed to the de-blocking equilibrium reaction and subsequent filtering of the
activator. The lowest filtering was observed at the lowest infusion temperature tested (110C).
However, the mechanical properties at this temperature were low compared to other infusion
temperatures. An optimum for the mechanical properties was found at 130C for the current
heating rate, indicating an optimum equilibrium between the blocked and de-blocked state of the
activator. If the heating rate of the composites could be increased, this optimum might be found at
a lower infusion temperature, with lower filtering as a result and thus more homogeneous
properties in the flow direction. Increasing the heating rate proved difficult for the heating method
currently in use.

2.4.2 Process optimization for vacuum infused APA-6 composites

In order to apply fibre-reinforced thermoplastic anionic polyamide-6 composites to large
structures, such as wind turbine blades, an optimisation of the infusion process for obtaining more
homogeneous properties is needed. Previous research on the isothermal infusion of the APA-6
composites (section 2.4.1 and [14]) focused on studying the effect of the infusion temperature on
the composite properties and their homogeneity in the flow direction. The isothermal infusion
strategy was of interest because a non-isothermal infusion was found to induce thermal and
chemical composition gradients in the flow direction and hence a gradient in the composite
properties (section 2.4.1 and [15]). This gradient, also present for the isothermal infusion but to a
much lesser extent, could be mainly attributed to the filtering of the activator, due to its deblocking reaction, and also to void formation in the flow direction. An optimum for the mechanical
properties was found at 130C for the current heati ng rate, which results from an optimum
equilibrium between the blocked and unblocked state of the activator. Therefore, an isothermal
infusion at 130C (infusion strategy 2 in see section 2.2.2) was used for the research presented in
this section, which main goals are:

Improving the degassing procedure in order to minimise the void content in the composite
Minimising the flow induced gradient by optimizing the process parameters during
infusion and post-filling
Finding the optimal flow conditions via different infusion velocities and pressures

Degassing Procedure
The presence of voids in composites is detrimental for several mechanical properties, especially
for matrix-dominated properties, such as interlaminar shear strength, compressive strength and
fatigue life [16]. Judd et al. [17] found that each 1% increase in void content induces a 7%
reduction in the interlaminar shear strength of the composite. This drop of the interlaminar shear
strength is approximately linear up to a total void content of 4%. A void content of 1% is generally
taken as the maximum acceptable value for structural applications [18]. A void content of about
8% was observed for the APA-6 composites and is, therefore, one of the major issues to address.
In previous research, degassing of the MMU tanks for 15 minutes at 100 mbar was proven
sufficient for infusing a void free neat polymer panel [10]. However, Tabel 3 shows that the same
degassing procedure leads to a void content of approximately 8% when applied to composites
(infusion according to infusion strategy 1). As a consequence, an alternative procedure was
investigated, consisting of degassing in the resin buffer for 5 minutes at 3 mbar. This way the void
content was reduced to about an average 5%. The resulting improvement in the composite
properties is clearly visible in the ILSS data presented in Figure 12.

12

Table 3. The effect of the degassing procedure on the composite properties.

Tmould
[C]
150
160
170
180

Degassed in buffer vessel (3 mbar, 5

minutes)
Conversion Crystallinity
Void
[%]
[%]
content [%]
92
48
2
96
41
6
95
38
7
93
32
2

Degassed in MMU (100 mbar, 15

minutes)
Conversion Crystallinity Void content
[%]
[%]
[%]
92
49
9
93
44
8
92
39
8
92
30
8

80
70
ILSS [MPa]

60
50
40
30
20

Degassed in buffer vessel

10

Degassed in MMU

0
140

150

160

170

180

190

200

mould temperature [C]

Figure 12. The effect of the degassing procedure on the inter laminar shear strength (ILSS)
of the composites.

Flow Conditions
To investigate the flow behaviour and identify the important parameters that influence the flow
and the quality of the composites, research was focused on the cross-sectional area of inlet tube
and on the infusion and post-fill (curing) pressures. The infusion and curing stages were analysed
separately. The infusion with activator T as the activator was done by infusion strategy 2, with an
infusion temperature of 130C and a cure temperature of 180C. For all the laminates
manufactured, the flow front position was monitored by means of a video camera. The camera
recorded the flow of the resin in flow direction along the right side of the laminate. From this
information, the flow rate could be calculated. The overall quality of the laminates was assessed
by non-destructive C-scan inspection, after which they were tested to obtain their physical and
mechanical properties. The baseline composites used in previous research (for both infusion
2
strategy 1&2) were infused with an inlet tube cross-section of 20mm and the infusion pressure
and post-fill pressure was set to 250 mbar, to obtain the same fibre volume fraction as melt
processed PA-6 composites. In this research, a full-factorial design was established in which the
following values were used:

Inlet tube cross-section: 4 and 20 mm

Infusion pressure: 3 and 250 mbar
Curing pressure: 3 and 250 mbar

Infusion stage
The infusion time was observed to be mainly dependent on the infusion pressure and not as
much on the inlet cross-section. For an infusion pressure of 250 mbar the infusion time was
5511s while for an infusion pressure of 3 mbar the infusion time was only 354s. The flow front
position and the flow rate through the fibre preform are shown in Figure 13. As it can be seen in
this graph, the flow is quite stabilised and mostly pressure driven from approx. 7.5 cm in the flow
direction. From the results displayed in Table 4, it could also be concluded that the infusion
pressure determines the thickness of the obtained laminate, regardless the post-fill vacuum
pressure. A thickness gradient, usually reported when using vacuum infusion [19], was not
present in these experiments.

13

Table 4. Thickness (t) and inter laminar shear strength (ILSS) near the inlet and outlet of the composites, and the infusion
times at different infusion and post-fill pressures.

Infusion
pressure
[mbar]
3
3
250
250

Post-fill
pressure
[mbar]
3
250
3
250

t
(inlet)
[mm]
2,69
2,71
2,75
2,76

t
(outlet)
[mm]
2,72
2,73
2,78
2,78

ILSS
(inlet)
[MPa]
48
47
48
55

ILSS
(outlet)
[MPa]
43
37
42
38

Difference
ILSS
[%]
10
19
12
31

Infusion
time
[s]
34,5
36
58,5
51,5

Curing stage
After infusion the inlet tube was closed, the temperature was raised to the required curing
temperature and the pressure was set to the post-fill pressure. The difference in mechanical
properties between the inlet and the outlet was found to be significant: a drop between 10 and
31% in the interlaminar shear strength over a length of 25cm was observed, as shown in Table 4.
To assess the cause of this gradient, the laminates were C-scanned (Figure 14) and crosssections in the flow direction were investigated by means of a field emission scanning electron
microscope.
25

Flow rate [cm 3/s]

20 mm2; 3 mbar
4 mm2; 3 mbar
4 mm2; 250 mbar

20
15
10
5
0
0

10

15

20

25

30

Flow front position [cm]

Figure 13. Flow front position during infusion and their corresponding flow rate at different inlet tube
cross-sections and infusion pressures.

The micrographs showed macro voids between the fibre bundles, mostly located in the upper part
when looking through the thickness of the laminates, to which the loss in mechanical properties
could be attributed. The C-scan images (Figure 14) showed that the highest infusion vacuum
pressure (3 mbar) resulted in a more uniform damping but a lower overall quality, while the lowest
infusion vacuum pressure resulted in a clear transition of the composite quality in the flow
direction. Likewise, the ultrasonic attenuation of the laminates near the inlet had a good
correspondence with the results of the ILSS tests.

3mbar-3mbar

3mbar-250mbar

250mbar-3mbar

250mbar-250mbar

Figure 14. C-scan results for different infusion pressures - post-fill pressures respectively, with an inlet tube cross-section
of 20mm2

14

Barraza et al. [20] reported that applying a post-fill pressure in a resin transfer moulding (RTM)
process reduced the void content significantly, independently of the infusion velocity, as it was
observed within this research. The higher post-fill pressure (3 mbar) led to an increase in
mechanical properties (tensile strength and stiffness) of at least 13%, which can be attributed to a
lower void content. When looking at the results for the ILSS in Table 4, it can be seen that the
post-fill pressure influences the mechanical properties, especially at the outlet as well as reduces
the gradient in flow direction.
Due to the low de-blocking temperature of activator T (125C), the infusion temperature of 130C
used in this research might result in filtering of the activator, inducing, as a result, a chemical
composition gradient in the flow direction. Therefore, the degree of conversion in the panels with
the highest difference in quality was measured and plotted in Figure 15. It can be seen that the
degree of conversion near the outlet is higher than that near the inlet in all the studied cases.
Likewise, it has approximately the same value for all infusion settings, which indicates that an
optimum resin constitution was found at the outlet. Near the inlet, more resin passed through the
fibre bed ensuring a proper wet-out and a better fibre-to-matrix bond, therefore reducing the
polymerisation, as explained in 2.4.1 and [14]. It could be concluded that mainly the amount of
resin that flowed through the cross-section influences the degree of conversion. Therefore, the
author suggests that flushing the laminate with extra resin after full wet-out could provide with a
better fibre-to-matrix bond in the whole laminate as well as more homogeneous properties in the
flow direction. However, such a procedure could lead to a lower overall degree of conversion.
Degree of conversion [%]

100
inlet
outlet

98
96
94
92
90
88
4-3-3

4-250-250

20-3-3

20-250-250

Figure 15. Degree of conversion near the inlet and outlet of the laminates at different inlet tube cross-sections [mm2] infusion pressures [mbar] - cure pressures [mbar]

Conclusions
In order to increase the homogeneity of the APA-6 glass fibre reinforced composites, an
alternative degassing method was investigated: after mixing the reactive resin, it was degassed in
the buffer vessel. This decreased the void content significantly and therefore resulted in better
mechanical and physical properties.
To minimise the flow induced gradient, the effect of several process parameters during infusion
and curing, namely the inlet tube cross section, the infusion and post-fill pressures, was
investigated. Although none of the considered combinations of parameters led to an outstanding
increase in the homogeneity of the composites, basic understanding was gained on the effect of
these settings in the overall quality of the laminates.
A fast infusion, corresponding to a high infusion vacuum pressure (3 mbar), was found to result in
a less visible flow gradient but also in a lower overall quality of the laminates. Therefore, research
on even lower infusion pressures (500 mbar) is highly recommended. It was also found that a
high post-fill pressure (3 mbar) led to a reduction in the void content, therefore resulting in an
increase in the mechanical properties of the laminates as well as more uniform properties in flow
direction. As for the physical properties of the laminates, a flow induced gradient was also visible
with a lower degree of conversion near the inlet. By flushing the laminate with extra resin after the
wet-out of the fibre preform, this gradient might be reduced.

15

2.5 Upscaling
Research aiming at upscaling the length of the laminates was based on an isothermal infusion.
For this study, activator C was used because the de-blocking temperature of this activator is
160C instead of 125C for activator T. It is thought that by using activator C, the gradient in flow
direction will be less significant than for activator T. The only drawback of using activator C is the
fact that its faster exothermal reaction once a certain temperature, at which the resin starts
reacting, has been reached within the system. This activator C will thus give more infusion
challenges for infusing long panels than activator T.
Isothermal infusion was already investigated in section 2.4. Results showed an improvement in
the uniformity of the laminate properties at 130C although some gradient in the flow direction still
remained, as shown in Figure 9. To check whether this lack of uniformity is just a local
phenomenon in the vicinity of the outlet or, on the contrary, it is induced by the flow itself, the
infusion length was increased from 25 to 45 cm, which is the maximum laminate length allowed
2
by the 50x50cm area of the infrared heating panels. Research was focused on the properties of
the resin and the composite as well as on the infusion strategy of these longer laminates. The
different infusions performed with this purpose are presented in Table 5.
Table 5. Infusion settings for the infusion of long laminates

Test nr.

1
2
3
4
5

Temperature of
resin in the buffer
vessel [C]
110
110
130
130
110

Temperature
of fibres during
infusion [C]
110
110
130
130
180

Infusion
pressure
[mbar]
3
250
250
250
250

Inlet clamped
after resin
reached outlet
Yes
No
No
Yes
Yes

Within this study, the infusion temperature that was chosen from the standpoint of the reduction
of the flow gradient of the laminates was 110C. For this temperature, the effect of the infusion
pressure was tested. This was done to investigate whether the effect that was seen in section
2.4.2 (lower visible flow gradient but lower overall quality for higher infusion pressures) was also
valid for the activator C system. For the lower infusion pressure (250mbar, test 2), the inlet was
not closed when the resin reached the outlet but was left open until the resin stopped flowing. The
laminate was heated up to the cure temperature from the moment that the resin reached the
outlet.
As an infusion temperature of 130C showed the best mechanical properties in combination with
an improvement in uniformity, it was chosen for the study on activator C as well. For this infusion
temperature, the effect of closing the inlet when the resin reached the outlet (test 3) or flushing
the laminate with extra resin during the heating phase (test 4) was investigated. During the
isothermal infusion, heating to the required temperature is started when the resin reaches the
outlet. Normally, the inlet is clamped just before the heating process starts. It is however thought
that flushing the laminate with extra resin during the heating phase might improve the properties
significantly since the product would be filled with extra resin if needed, diminishing by that the
number of voids.
To see whether it was possible to infuse long panels with the non-isothermal infusion (infusion
strategy 1), a high cure temperature (180C) was chosen as this is the most critical test case. At
this high temperature, the cure of the resin will start fast and the exothermic reaction will increase
the viscosity of the resin quickly, therefore hindering the resin flow in the long panel.
For all the tests, the infusion time that was needed for the resin to reach the outlet was noted and
C-scan images were made.

16

Tests 1 and 2 were done to check whether the effect of the infusion pressure was also valid for
the activator C system at an infusion temperature of 110C. It was found that increasing the
vacuum infusion pressure to 3 mbar slightly reduced the flow induced gradient while it did not
affect the overall quality of the laminates, even when the inlet was clamped after the resin
reached the outlet.
The optimization of the infusion temperature as described in section 2.4.1 was performed for the
resin system with activator T. The results of tests 2 and 3 provided information about the effect of
the infusion temperature for the activator C system (see Figure 16 and Figure 17 respectively for
the results of the C-scan inspection). As it can be seen in these figures, the quality of the
products and the flow gradient is comparable for both infusion temperatures, although the best
result in reducing the flow gradient while maintaining a good overall quality was obtained with the
infusion temperature of 130C. This result does not entirely agree with those in section 2.4.1,
where a clear improvement in flow gradient was observed for the mechanical properties at low
infusion temperatures, 110C, but a better quality at the higher infusion temperatures. It can be
concluded then that due to the high de-blocking temperature of the activator C, the flow gradient
and quality of the composite is less dependent on the infusion temperature.

Figure 16. C-scan

results for infusion
temperature of 110C
when inlet is not
clamped during heating
(test 2)

Figure 17. C-scan results for infusion temperature

of 130C when inlet is not clamped during heating
(test 3)

Figure 18. C-scan results for inlet clamping after

infusion (test 4)

Flushing the laminate with extra resin was performed in tests 2 and 3 by leaving the inlet open
during the heating process. In test 3 and 4, the only parameters that was changed, was the
clamping of the inlet right after the infusion. The C-scan inspections corresponding to tests 3 and
4 are displayed in Figure 17 and Figure 18 respectively. It can be seen that the flow induced
gradient is significantly reduced and that the overall quality of the laminates improved significantly
when the resin is flushed during heating. One of the panels manufactured with the parameters of
test 4 did not even show any flow gradient, which is the one of the goal of the optimization of the
process in combination with a good quality of the laminate.
Table 6. Infusion times for the infusion of long laminates

Test nr.

1
2
3
4
5

Temperature of
resin in the buffer
vessel [C]
110
110
130
130
110

Temperature
of fibres during
infusion [C]
110
110
130
130
180

Infusion time
[sec]
197
269
245
180
144

The infusion times for all the tests are also shown in Table 6. It can be seen in this table that
increasing the infusion temperature, decreases the infusion time. Due to the high heat

17

conductivity of the fibres compared to the resin, the resin that is infused into the 180C fibre
preform will quickly heat up, lowering the viscosity of the resin and facilitating the infusion.
However, due to this high temperature, the resin will start its reaction faster after infusion. An
optimum for the time available for the infusion process is therefore expected to be found at lower
infusion temperatures. It was also observed that a lower infusion time resulted in a better quality
of the composite. When the infusion time of the 180C laminate (144 sec) is compared with that
corresponding to a shorter flow length of 25cm (75 sec, [4, p.148]) a linear increase of the
infusion time with the flow length can be ascertained.
The laminates that were infused at 110-130C while letting the resin flow through the laminate
while heating up to the cure temperature of 180C, showed a good quality. This result was
achieved without increasing the infusion time into the laminate. It can therefore be concluded that
the up-scaling of the laminates is feasible.

2.6 Cure
Research on post-processing of anionic polyamide-6 composites was performed, consisting of
two main areas of interest: the cure time and the anneal cycle, discussed in section 2.6 and 2.7
respectively. The cure time is the time that the product is at the cure temperature. The anneal
cycle is the heat treatment that is given to the laminate once it is cured and cooled down. This
annealing cycle can be done at different temperatures and for different times. The cure time and
annealing temperature proved to be the crucial parameters to increase the degree of crystallinity,
minimise the residual stresses and hence improve the mechanical properties.
The effect of the cure time is assessed on both neat resin and composites. For the neat resin, a
broad spectrum of cure times was tested ranging from 15 to 120 minutes, with a 15 min interval
with an extra data point at 180 min. Glass fibre reinforced APA-6 were cured at 30-60-90-120min,
firstly to determine if the trends in material properties correlate to the neat resin samples and
secondly to determine optimum cure time.

100

35

Degree of conversion [%]

Degree of crystallinity [%]

Pure resin
For the pure resin, it was seen that with increasing cure time, the degree of crystallinity rose, until
a plateau was reached at approximately 100 minutes of curing, as can be seen in Figure 19. The
cure time as researched by van Rijswijk et al. [10], had little effect on the degree of conversion
between 30 and 45min, over a range of cure temperatures. The results from this research show a
clear agreement in an approximately constant DOC of 92% between the 30 to 75min range.
Figure 20 also shows an optimum in degree of conversion at the same cure time as for the high
degree of crystallinity. The almost 7% change in conversion observed over a cure time range of
75min to 120min clearly indicates that further conversion of monomer, at a cure temperature of
180C, can take place for neat resin. After that, t he degree of conversion decreases due to
degradation of the polymer or due to a shift in the equilibrium reaction between the monomer and
polymer.

33
31
29
27

95

90

85

80

25
0

50

100

150

200

Cure time [min]

Figure 19. Evolution of degree of crystallinity of pure resin
in time.

50

100

150

200

Cure time [min]

Figure 20. Evolution of degree of conversion of pure resin

in time.

18

37

Short-beam strength [MPa]

Degree of crystallinity [%]

Laminates
For the production of the laminates, infusion strategy 1 was used. The effect of cure time on the
laminate is greatly less significant for the degree of conversion, which proofed to be almost
constant at a value of 98.5%0.3%. For the effect of cure time on the degree of crystallinity,
Figure 21 shows a linear increase to a peak value of 36.5% at 90min and an almost constant
peak crystallinity of 36% even at 120min. Figure 22 shows that the maximum short-beam strength
is 77.4MPa, coinciding with the cure time of 90min for peak crystallinity.
36
35
34
33
32
31
0

30

60

90

120

150

80
75
70
65
60
55
50
0

Figure 21. Degree of crystallinity for different cure times

30

60

90

120

150

Cure Time [min]

Cure time [min]

Figure 22. Short-beam strength for different cure times

The increase in crystallinity with cure time is in the same order of magnitude as for the pure resin.
The increased crystallinity for both the pure resin and the laminate can be explained by the
greater extent of primary crystallization that occurs during curing over the secondary
crystallization that only initiates from subsequent cooling. It is known [10] that at higher
processing temperature branching may occur in the resin. Branching causes a crystal type
transition from to structure [21-22], which are two types of crystals with different levels of
perfection. With an increased primary crystallization, a greater amount of the more perfect
crystals are formed, while or the less perfect crystals formed during secondary crystallization
make up a lower composition of the overall crystal structure. An inherently greater extent and
perfection of the crystal structure in the polymer clearly would increase the strength of the
polymer due to increased covalent bonds present.
It was observed that an optimal degree of crystallinity could be found and that this cure time
corresponded to optimal mechanical properties (short-beam strength). Literature states that all
semi-crystalline polymers have a direct relationship between the short-beam strength and the
degree of crystallinity [23]. This direct relation further accounts for the results showing an
increase in the short-beam strength of the laminate due to the increased crystallinity with cure
time.
Conclusions
An increase in degree of crystallinity was found with increasing cure time until an equilibrium
value was reached. The results were comparable for the pure and the fibre-reinforced APA-6,
with a max increase of 15% after approx. 90 minutes of cure. The mechanical properties
followed the same trend, having a peak value (77.4MPa) at the cure time with the maximum
degree of crystallinity.

2.7 Post processing of APA-6 composites

In previous research on pure APA-6 [10], it was shown that the polymerisation process was
completed within 30 minutes. At the end of polymerisation, however, the crystallisation is still in
progress. As the properties of the resin are mainly driven by the level of crystallinity [10], the cure
and/or annealing cycle may influence the composite properties significantly. By selecting the right
curing and post-processing parameters, it is expected that the demoulding time can be optimised,
residual stresses minimised and hence the neat resin and composite properties significantly
improved. The influence of annealing parameters will be studied.

19

All the samples in this study were manufactured at a processing temperature of 180C, infused by
strategy 1 (see section 2.2.2). At this temperature, polymerisation precedes crystallisation. When
compared to lower processing temperatures, this processing temperature yields a low degree of
crystallinity and has high residual stresses, due to thermal shrinkage [24] after a normal cure
cycle. Therefore, it is thought that the post-cure cycle will have the largest effect when the
samples are manufactured at this processing temperature.
Annealing conditions
Initial cure times of 30 and 60 min were chosen for the research on annealing of APA-6
composites. As seen in the last paragraph, full crystallisation has not been reached yet for those
cure times. It is expected that the crystallization behaviour will improve and the residual stresses
will diminish during the annealing cycle.
Within this study, the cured laminate is cooled down to room temperature and removed from the
mould, after which it is placed in an oven for the annealing cycle. Design of Experiments (DoE)
was used for this research. DoE is a method that is used to determine the relationship between
the different parameters affecting the process (annealing time, annealing temperature, rate of
cooling after annealing process) and the results of that process (change in crystallinity and in
mechanical properties during the annealing process.
Three important temperatures can be identified for annealing: the glass transition temperature Tg
(60-75C), the crystallization temperature Tc (160-175C) and the melting temperature Tm
(210-220C). Semi-crystalline materials are known to undergo additional crystallization when
held at a temperature between its glass and melting temperature. Conventional annealing is done
at temperatures at or above Tc, leading to increased crystallinity and reduced toughness [25]. If
embrittlement is undesirable, a lower temperature annealing can be effective. A lower annealing
temperature reduces the heat energy requirements without extending annealing time and thus
reducing the costs. The following temperatures were selected for this study: 100-150-175C. The
laminates were held at the annealing temperature for 2, 4 or 6 hours. Temperatures at or above
200C will not be explored in this study as thermal and thermal-oxidative degradation is
considerably high [26] and cannot be used practically especially with significant material
discoloration.
After the annealing cycle, the laminate is subjected to a controlled cooling of either fast or slow
rate. Fast cooling, is performed by removing the laminate from the oven and allowing it to cool
naturally to room temperature. Slow cooling, is carried out by switching off the oven and allowing
the laminate to cool inside the oven, with the oven ventilator opened.
Annealing results
Degree of conversion
For reinforced APA-6, the effect of reheating the polymer for a period of time is expected to
increase the degree of conversion, improve the crystallinity by inducing favourable crystal type
transition (from -crystals to -crystals) [27] and remove imperfections in crystal structure. The
degree of conversion, however, seemed to be constant for all laminates, complying with the
results of van Rijswijk et al. [10], stating that the conversion of the APA-6 resin is completed or
stops within 30 minutes.
Degree of crystallinity
For every laminate, crystallinity samples were taken before and after annealing. The relative
change in crystallinity [%] in relation to the annealing temperature is presented in Figure 23. The
results presented here are the averages of all the annealing times and rates of cooling at a
certain annealing temperature. Hereby, the main effects due to a change in parameter in the
process can be seen. The mean crystallinity for un-annealed samples is 32.13% after 30 minutes
of cure and 29.6% after 60 min. It can be seen that for both curing times, the crystallinity
increases significantly with increasing annealing temperatures, whereby the biggest increase is
found around the crystallization temperature of the laminate. It is known that crystalline polymers

20

heated to temperatures slightly under melting temperature results in increased lamellar crystal
thickness due to sufficient thermal energy given to the polymer that enables molecular motion
[28].
35
60 min cure

25

30 min cure
20
15
10
5
0
-5

75

100

125

150

175

200

Change in crystallinity [%]

Change in crystallinity [%]

30

60 min cure
30 min cure

30
25
20
15
10
5
0

-10

Annealing temperature [C]

Annealing time [hr]

Figure 23. Change in crystallinity at different annealing

temperatures (averaging the results for different annealing
times and cooling rates at the different annealing
temperatures).

Figure 24. Change in crystallinity at different annealing

times (averaging the results for different annealing
temperatures and cooling rates at the different annealing
times).

Gogolewski [29] outlines the fact that recrystallization of the polymer proceeds at a faster rate at
higher temperatures due to the increase in the number of dislocations in the crystal structure,
which forms very favourable nucleation sites. Furthermore, the release of topological constraint
and stresses in the amorphous phase at higher temperature promotes crystallization [27]. The
thermal energy seems crucial in the annealing process, as temperatures close to the Tg do not
show an increase in crystallinity. Gogolewski et al. [29] observed that having a lower annealing
temperature reduces the post-processing effectiveness on the nylon-6. For the annealing at
100C in this study, even a decrease in crystallinity was seen, see Figure 23. This result can not
be explained at this moment.
In Figure 24, the change in crystallinity with respect to the annealing time is shown (averaging the
results for different annealing temperatures and cooling rates at the different annealing times). As
can be seen in this graph, no significant effect could be identified. For the annealing study on
melt-processed PA-6 [29], experiments were performed at 20-50-60-2000hrs at various
temperatures up to 215C. An incubation period of 1 0hrs was noted at temperature of 215C to
see a change in the long spacing of SAXS experiments. An even longer incubation time (20hrs)
was noted at 200C after which material properties started to improve significantly. It can
therefore be concluded that the results in this study, for the lower annealing temperatures, do not
give any significant results at this point, but if the annealing time is increased it might show an
increase in polymer properties.
A reduction in the cooling rate after annealing, keeps the polymer chains mobile for a longer
duration, which allows more time to form crystals and thus increase the crystallinity of the polymer
or increase the level of perfection of the crystals. The cooling rates of the laminates are non-linear,
unlike the heating rates to the annealing temperature. As can be seen in Figure 25, the cooling
rates show the same trend when plotted against their annealing temperature. In this annealing
study, the cooling rate appears to be less significant however, as can be seen in Figure 26. As
the polymer chains have sufficient thermal energy for crystal formation during the annealing
phase, less can be gained from a slow cooling rate at the end.

21

0
100

125

150

175

35

200

-4

Change in crystallinity [%]

Cool down rate [C/min]

0
-2 75

-50

-6
-8

-100

-10
-150

-12
-14
-16

-200

slow cooling

-18

fast cooling

-20

-250

30
25
20

Slow

15

Fast

10
5
0

Anneal temperature [C]

Cooling rate

Figure 25. Cooling rates at different annealing

temperatures.

Figure 26. Change in crystallinity for different cooling rates

As can be concluded from these results, the annealing temperature is the key factor for an
increase in crystallinity for both curing times.
Short-beam strength
The results for the short-beam strength with respect to the annealing temperature (see Figure 27)
do not show the same trend as for the degree of crystallinity for a cure time of 60 minutes. A peak
value of 72.6 MPa was reached for the 60 min cured laminate, compared with the 70.8 MPa
obtained with an un-annealed sample. However, for the 30 min cured laminate, the same trend
was seen as for the change in crystallinity, going from a baseline of 59.6 MPa to a maximum of
69.32 MPa. The biggest difference between the two cure times is that the fibre-to-matrix bond, its
intertwining with the bulk matrix and the degree of branching in the bulk are less for the 30 min
cured laminates. It can thus be concluded that the degree of crystallinity is not the only parameter
determining the mechanical properties. By annealing, the structure of the polymer chains is
improved, the amount of dislocations reduced and a more entangled network formed, leading to a
more distinct increase in mechanical properties after annealing a 30 min. cured laminate when
compared to a more perfect laminate (60 min of cure).
The same observation was done when looking at the annealing times, see Figure 28. The effect
of the annealing time is not significant for the 60 min. cured laminate unlike for the 30 min cured
one. For the 30 min. cured samples, the longer the laminate is held at the annealing temperature,
the bigger the increase in mechanical properties. After 30 min. of cure, more imperfections will be
present in the matrix as well as a lower fibre-to-matrix bond and less branching. The annealing
time therefore becomes an important factor in the increase in mechanical properties.

75

Short-beam strength [MPa]

Short-beam strength [MPa]

The effect of the cooling rate proved to be insignificant for the mechanical properties, which is in
agreement with the results for the change in crystallinity.

70

65

60
60 min cure
30 min cure
55

75

70

65

60
60 min cure
30 min cure
55

75

100

125

150

175

200

Annealing temperature [C]

Figure 27. Short-beam strength for different annealing

temperatures.

Annealing time [hr]

Figure 28. Short-beam strength for different annealing time

s.

22

Conclusions
The results for the study on the annealing cycle showed that the change in degree of crystallinity
depended mostly on the annealing temperature. The biggest improvement was seen near the
crystallization temperature of APA-6 (175C) with an increase in crystallinity of 20-30%. It was
also observed that the mechanical properties only followed the same trend as the crystallinity
behaviour for the laminates cured for 30 minutes, leading to a significant improvement in shortbeam strength (+17%), as big improvements could be reached with respect to fibre-to-matrix
bond and branching of the matrix. As these properties were already attained during curing for a
60 min laminate, their mechanical properties did not show the same trend as its crystallinity after
annealing, showing only a slight increase (+3%) in short-beam strength
It could be concluded that the selection of the long cure time is most effective for obtaining good
mechanical properties in combination with a high degree of crystallinity. The same properties
could be obtained with an annealing cycle, although requiring more time in a heated oven and
thus more heating energy.

2.8 Conclusions
In this chapter, the process optimization of thin glass fibre reinforced APA-6 composites was
discussed. First of all, the effect of the pot life (time and temperature) on the reaction/reactivity of
the resin as well as on the increase of the viscosity was investigated. It could be concluded that
the longer the residence time and the higher the initial buffer vessel temperature, the higher the
initial viscosity and the faster the reaction respectively, hence, complicating the infusion of large
products. Investigating the effect of this residence time or pot life more fundamentally by means
of reaction kinetics is seen as a critical part in the investigation on the infusion of large wind
turbine blades.
Secondly, the effect of the infusion itself was tested. Different infusion strategies were tested in
order to increase the homogeneity. To overcome thermal and chemical composition gradients, an
isothermal infusion strategy was implemented for the high temperature vacuum infusion process.
Research was done on the infusion temperature to study its effect on the composite properties
and their homogeneity in flow direction. It was seen that at all infusion temperatures, there was
still filtering present. A trade-off needed to be made between low filtering (low infusion
temperatures) and high mechanical properties (higher infusion temperatures). With the current
heating rate, the optimum was found at an infusion temperature of 130C. As the current heating
methods did not allow a faster heating rate between the infusion and cure temperature, research
was focused on minimizing the flow induced gradient and finding the optimal flow conditions The
effect of different process parameters, like the degassing procedure, the infusion pressure
(infusion velocity) and cure pressure (post-filling) were studied. Degassing the resin in a buffer
vessel after mixing decreased the void content significantly and therefore resulted in better
mechanical and physical properties. A high infusion velocity caused a lower gradient in flow
direction, but resulted in a lower overall quality compared to the lower infusion velocity. Applying
a post-fill pressure after infusion proofed to reduce the void content and therefore increasing the
mechanical properties and reducing the flow induced gradient.
The effect of increasing the flow length of the infusion was tested. All laminates were fully infused
without changing the processing parameters and resulted in good quality laminates. It can
therefore be concluded that the up-scaling of the laminates is feasible. It was seen that there was
a linear increase of infusion time with flow length. Flushing the laminate with extra resin during
the heating up phase in the infusion process resulted in a laminate with a significant reduction, or
even disappearance of the flow gradient.
And finally, the effect of a post-cure or post-processing was investigated. For the research on the
cure parameters, it was seen that the optimum in mechanical properties was found at a cure time
of 90 minutes which corresponded to the maximum in degree of crystallinity. The results for the
study on the annealing cycle showed that the change in degree of crystallinity depended mostly

23

on the annealing temperature. The biggest improvement was seen near the crystallization
temperature of APA-6 (175C) with an increase in crystallinity of 20-30%. It was also observed
that the mechanical properties followed the same trend as the crystallinity behaviour for the
laminates cured for 30 minutes, leading to a significant improvement in short-beam strength. It
could be concluded that the selection of the long cure time is most effective for obtaining good
mechanical properties. The same properties could be obtained with an annealing cycle, although
requiring more time in a heated oven and thus more heating energy.

24

3 Thick laminates: Heating methods

3.1 Introduction
The isothermal infusion strategy, as described in section 2.4.1., showed a lot of potential for the
infusion of large APA-6 composites. Due to the low infusion temperature of both the resin and the
fibres a long infusion window is obtained while obtaining good mechanical and more uniform
properties. The study on the isothermal infusion strategy was focused on thin laminates.
However, if this strategy is wanted for the infusion of thick laminates, it needs to be researched
whether the heating of the whole product from the infusion temperature to the cure temperature is
feasible, especially with the low heat conductivity of the resin material. The heat inside the
product needs to reach the required polymerization temperature before the resin starts its
exothermal reaction. Otherwise, the reaction will start at a lower temperature than the required
temperature for best quality; good resin and mechanical properties. It is expected that with the
current heating method a temperature gradient will arise through the thickness of the product, as
the inside of the laminate is heated by conduction. In this chapter, different heating methods will
be tested and will be compared to each other. The heat distribution through the thickness of the
laminates and the heating rate from the infusion temperature to the curing temperature will be
considered.

3.2 Experimental
3.2.1 Materials
Resin material
The resin materials used are described in section 2.2.1. In this research, the activator C is used
for the infusion of the thick-walled composites.
Glass fibres
E-glass fibre mats are used to reinforce the APA-6 composites. In the research for the thickwalled composites are coarser weave is used than compared to the 8HS glass fabric used in the
study of the thin laminates. The coarse 5 mm wide 12k tow plain woven glass fabric (RP0840)
was supplied by Ten Cate Advanced Composites with the same fibre sizing as on the 8HS weave.
The coarse weave had a high permeability resulting in a fast infusion.
Mould material
For the infrared heating, which is one of the heating methods investigated in this chapter, it is
important to test the influence of the surface finish of the aluminium mould used in the set-up on
the absorption of the infrared radiation. Therefore, moulds were prepared with different surface
treatments and tested, as will be discussed in 3.3. A 1.5 mm thick mould with a black paint finish
was used for all the moulds used in this research after this investigation.

3.2.2 Processing methods

To investigate the heating rate through the thickness of the laminates, a laminate of considerable
thickness is tested. All heating methods were tested on a balanced, symmetric 40-ply laminate
2
(22x22cm ), see Figure 29, resulting in a thickness of 24 mm once consolidated. The vacuum bag
is made as described in section 2.2.2.
Infusion strategy
The infusion strategy is the infusion strategy 2 as described in section 2.2.2. Before the infusion
takes place, the thermocouples are connected to Keithley Temperature Logging Computer to
record the temperatures during heating. All tests are done with an infusion temperature of 110C
and the laminates are cured at a temperature of 180C. Heating from 110C to 180C is
considered to be the maximum temperature range possibly needed for the production of APA-6

25

laminates and in this 70C heating step, the capaci ty differences between the heating techniques
will become clear.

Figure 29. Vacuum infusion bag for thick laminates with the
coarse fabric weave

Figure 30. (Kapton) Thermofoil Heater

Heating devices
Infrared panels
2
Two 5000 watts infrared emitters of 50x50cm are used, as can be seen in Figure 4. They are
provided by Watlow USA. Two PID controller are used to control the top and bottom panels. A
thermocouple is placed on the surface of the kapton foil and on the mould to be used as the
control input. Before infusion, the power controller was tuned for optimal heating of the dry
laminate.
Heated press
The heated plate consists in two aluminum blocks heated by tubular heating elements. The power
2
output is 3000 Watt over an area of 25x25cm (4.8W/cm ). Three elements are inserted in each
block.
Thermofoil
Another contact heating method was tested, namely a thermofoil. This Polyimide (Kapton)
Thermofoil Heater is sold by Minco Products inc., USA. The kapton foil protects the heating
2
system from the chemicals in the process. A 10x10cm sized flexible foil with a thickness of 0.3
mm was purchased and used in this research. The thermofoil was used on the mould side where
2
the fibres are placed. The power of the thermofoil is 1.8W/m . To avoid heat loss through the
aluminium plate, isolation material was installed. The heating device for the top of the vacuum
bag was the infrared panel as described above.
Resistive mesh
As the heating rates for the surface heating turned out to be not sufficient, a heating source from
the inside out needed to be implemented. A metal mesh will be used as a heating device in the
middle of the fibre lay-up to provide resistive heat from the inside out while heating up the
laminate from infusion to curing temperature. The resistivie mesh consists of RVS steel wires
(thickness: 200m, width: 858m) provided by Dinxperlo Wire Weaving Co Ltd. This heating
source is placed in the middle of a laminate, see Figure 31. Since the temperature of the metal
mesh had to be controlled to the infusion and polymerization temperature, the power controller
was adjusted manually to the desired temperature by manual adjustment by varying either the
applied voltage or amperes. First, a high power input is given for the maximum heating rate to the
required temperature and when this temperature was reached, the power was slowly reduced
until a constant temperature. The laminate was produced in combination with the infrared heating
from the outside.

26

Carbon fabric
As carbon fibres exhibit a high thermal conductivity, it was also tested as a heating source in the
middle of the laminate. It can be heated up in two ways by induction or by direct voltage. Direct
voltage will be used in this study. Although it might be advantegeous from a hardware point of
view to test the induction heating in the future. A power supply was connected to a plain weave
carbon fabric. The carbon fabric was clamped between two copper plates to connect the fabric to
the wire of the power supply for good connectivity and good heat distribution, see Figure 32. The
wire was soldered to one of the copper plates and connected to the power supply. The power
controller was also adjusted manually to the desired temperature by manual adjustment by
varying either the applied voltage or amperes. First, a high power input is given for the maximum
heating rate to the required temperature and when this temperature was reached, the power was
slowly reduced until a constant temperature. The laminate was produced in combination with the
infrared heating from the outside.

Figure 31. Position of the resistive mesh in the

middle of the fabric lay-up and its connection to the
power supply

Figure 32. Connection of the carbon fabric via two copper plate to
the copper wire of the power supply

3.2.3 Analysis methods

Temperature measurements
Through the thickness of the laminate, K-type thermocouples were placed to record the
temperature during the infusion and the cure. The position of the thermocouples can be seen in
Figure 33. Heating experiments are performed on the dry fibre lay-up prior to infusion to check
the heat distribution through the thickness without the exothermic reaction of the resin. During
infusion and heating to the required curing temperature, the temperatures are also logged.

Figure 33. Position of the thermocouples through the thickness of the lay-up.

Viscosity measurements
Viscosity measurements were done, as described in section 2.2.3., to select the required heating
rate.
Reaction kinetics
Reaction kinetics tests were performed to investigate the temperature build-up. To simulate the
adiabatic conditions of the polymerization in thick laminates, a wide 600 ml beaker (VWR 2131174) was used as a mould. For ensuring a nitrogen protective environment during the whole
polymerization, a cover lid was designed. The lid has two small holes for rigid thermocouples, one
in the middle, for adiabatic conditions, (inner thermocouple) and the second one on the side

27

(outer thermocouple). On the left side of Figure 34, there is a connection for nitrogen. Also, the
design of a supporting aluminium plate to hold one beaker was necessary.

Figure 34.Glass beaker with cover lid and supporting plate

The polymerization mixture was prepared as described in section 2.2.1. The glass beaker with
the reactive mixture was transferred into the first oil bath, which was set to the same temperature
as mixture in the MMU, for simulation of the pot life and of the time to infuse the thick laminates.
After 5 minutes, the beaker was placed into the second oil bath set to a higher temperature for
the polymerization reaction to take place, simulating the heating phase of thick laminates by
contact heating. The cover lid was then placed over the beaker and the temperature
measurements, as described above, were started. The thermocouples were lubricated by grease
for easier removing from the product after reaction.

3.3 Heat distribution

In this section, the heating profiles through the thickness of the laminates and the heat distribution
will be discussed. In the next section (3.4) a comparison will be made between all the heating
method comparing the heating rate of the slowest and the fastest layer in the laminate. From the
viscosity measurements and adiabatic temperature build-up could be estimated. As can be seen
from Figure 35, the viscosity increase for the resin mixture used in this research is highly
dependent on the processing temperatures.
1,2

Viscosity [Pa.s]

1
0,8
0,6
0,4
2--2 160
2--2 170
2--2 180
2--2 130

0,2
0
0

10

15

20

-0,2
Time [min]
Figure 35.Viscosity measurements at different mould temperatures

These viscosity measurements were done with a mould that was already at the curing
temperature of the product. For a cure temperature of 180C, an infusion window of three minutes
is seen, while for a cure temperature of 130C, the reaction starts after 12 minutes (initial viscosity
build-up) reaching an infusion window of 15 minutes.
During the heating phase from 115 to 180C, the average temperature of the resin over the
heating time is 145C. If a linear relationship with mould temperature is assumed for the viscosity
build-up, the reaction at 145C would start at approx 8.5 minutes.

28

The adiabatic reaction kinetics test is more representative for the production process of the thickwalled laminates. An infusion time of 5 minutes is assumed during the test at an infusion
temperature of 115C after which the product is heated by contact heating (oil) to the required
curing temperature. It can be seen (Figure 36) that for a cure temperature of 160C, the reaction
starts to build up exothermal heat fast after 10 minutes. It is also clear from this figure that the
reaction already starts before the cure temperature is reached.
The start of the temperature build-up obtained from the adiabatic measurements could be
considered as the maximum heating time preferred for the infused laminate. From the results at
140, 150 and 160C, it could be seen that a linear relationship between the start of the
temperature build-up and the cure temperature is a safe way of extrapolating the results to a
higher temperature. The start of the reaction at 170C would be extrapolated to 8.3 minutes and
at 180C about 6.6 minutes. It could be concluded that the required heating time from 115 to
180C would be around 6.6-8.3 minutes.
200
190

Temperature [C]

180
170
160
150
140

140

130

150

120

160 (1)

110

160 (2)

100
0

200

400

600

800

1000

1200

1400

Time [sec]

Figure 36. Adiabatic temperature measurements with an initial pot life of 5 minutes at 115C, cured at different
temperatures

3.3.1 Heated press

As can be seen from the heating profiles through the thickness of the laminate in Figure 37, the
layer that heats up the slowest is the middle layer of the laminate. For the middle layer, 20
minutes were needed to heat the resin from 110 to 180C, which is too slow for a good reaction.
Furthermore, it could be concluded that there is a good heat uniformiuty around the centre.
However, the heated platen is considered to be a non suitable heating method for curing thick
laminates.
Heated press temperature transition
200
190
180
Temperature (C)

170
Top

160

30

150

25
140

Middle

130

15
10

120

Bottom
110

Under mold

100
0

8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42
Time (min)

Figure 37. Heating profiles through the thickness of the laminate during heating from 110 to 180C with the heated platen

29

3.3.2 Infrared
The influence of the surface finish of the aluminium mould on the absorption of the infrared
radiation was tested prior to the heating experiments with the infrared heating. Therefore, moulds
with different surface treatments were tested: an untreated mould, a sanded mould, a mould with
a black paint finish and an anodized mould. Also different thickness were tested; 2 and 6 mm.

Figure 38. Heating profiles of different mould plates using the infrared panels as heating device

It can be seen from Figure 38 that the reduction in thickness leads to a significantly faster heating,
as expected. The difference between the untreated and black painted surface can be clearly seen
for the 2 mm thick mould plate in which the advantage of using a black paint finish is proven. Also
compared to the other surface finishes, the black paint seems to increase the infrared absorption
the most.

Figure 39. Heating profiles through the thickness of the laminate during heating from 110 to 180C with the infrared panels

The results for the heating profiles using the infrared panels as a heating device are shown in
th
Figure 39. The middle of the laminate and the 15 layer show a similar temperature behaviour,
showing a non-symmetric heating behaviour throught the thickness of the laminate. 12 minutes
were needed to heat up the whole laminate to 180C, which is considerably faster than the

30

heated platen press. However, from a polymerisation reaction point of view, this heating rate is
still too slow.

3.3.3 Thermofoil
200
190
180
Temperature (C)

170
160
150

top kapton
40
30
25
20
15
10
Under mold

140
130
120
110
100
0

12

16

20
24
28
Time (minutes)

32

36

40

44

48

Figure 40. Heating profiles through the thickness of the laminate during heating from 110 to 180C with a thermofoil on the
mould side and an infrared panel at the top

For the test with the thermofoil as a heating device, the top part of the vacuum bag was heated
with the top infrared panel. A non-symmetric heating distribution can be observed in Figure 40. To
have a better look to the performance of the thermofoil, these results are compared with the
double IR panel experiment, see Figure 41. The top layer shows the same temperature behaviour
for both heating methods as can be expected for the same heating device. The biggest difference
can be found for the bottom layer. It can clearly be seen that the thermofoil is more powerful.
However, this difference can not be seen in the slowest heated layer, the middle. Here, the
heating curves look similar again. Although the chemical reaction of the laminate heated by the
double infrared panels starts earlier.

200

Temp. (C)

180
160
140
120
100
0

10

11

12

13

14

15

Tim e (m in)

Thermofoil+IR 40

Thermofoil+IR 20

Thermofoil+IR 0

Double IR 40

Double IR 20

Double IR 0

Figure 41. Comparison of heating profiles of laminates heated by double infrared, or by thermofoil in combination with the
top infrared panel.

The thermofoil has a good heating rate. Its small thickness and the fact that it is a resistive
heating element provide a very efficient solution with minimal hardware. Due to the low thermal
conductivity of the resin, that heat however is not conducted to the laminate. Hence the heating
rate is still not enough for heating the laminate to the required curing temperature. A crosssection of the cured laminate can be seen in Figure 42.

31

Figure 42. Cross-section of a cured 24 mm thick laminate heated by thermofoil in combination with the top infrared panel.

3.3.4 Resistive mesh

Both the infrared panels and the resistive heating mesh were used in this experiment, in which
the temperature of the resistive mesh is controlled manually to the required temperature. 45
amperes were applied to the mesh. The layer that is heating up the fastest is now the middle
layer, see Figure 43, where the resistive mesh is located. It reached the cure temperature at 2
min 40 seconds. A cross-section of a 24 mm thick laminate that was heated with a resistive mesh
can be seen in Figure 44.
190
180
170

Temp. (C)

160
Top

150

30 layers
140

25 layers
Middle

130

15 layers

120

10 layers

110

Bottom

100
0

5
6
Time (min)

10

11

Figure 43. Heating profiles through the thickness of the laminate during heating from 110 to 180C with a resistive mesh in
the middle of the fibre lay-up and the infrared heating as surface heating

It could be concluded that using a resistive mesh is a suitable solution for heating the laminates
from the inside out. The interaction of the mesh with the galss fibres and the resin needs to be
investigated, as well as the application of the mesh as a heating method in case of heating up a
large wind turbine blade.

Metal mesh

Carbon fibres

Figure 44. Cross-section of laminates heated by a metal mesh or a carbon fabric in combination with the intrared panels

3.3.5 Carbon fabric

When the carbon fabric is used as the inside heating method in combination with the infrared
panels to heat up the laminate, it can be seen the middle layer heats up the fastest to the curing

32

temperature (in 1.5 minutes). This result, see Figure 45, is similar to the result obtained with the
resistive mesh, as described in section 3.3.4. A cross-section of a 24 mm thick laminate that was
heated with a carbon fabric in the middle can be seen in Figure 44.
190
180
Temperature (C)

170
160
Top

150

30 layers

140

25 layers

130

Middle
15 layers

120

10 layers

110

Bottom

100
0

4
5
Time (minutes)

Figure 45. Heating profiles through the thickness of the laminate during heating from 110 to 180C with a resistive carbon
fabric in the middle of the fibre lay-up and the infrared heating as surface heating
th

The slowest layer is the 10 layer in the lay-up and reaches the curing temperature after 8
minutes, which is an acceptable heating time for the reaction of the APA-6 resin. To check the
heat distribution through the thickness, two graphs were made. The first graph, Figure 46 shows
the heating profiles of the heat input layers, while in Figure 47 the heat distribution throughout the
other layers is shown. It can be seen that the infrared heating profiles are similar to each other
and that the heat distribution is symmetric throughout the thickness of the laminate.
200

200

180

180

160

160

140

Top
Middle

140

120

Bottom

120

100

30 layers
10 layers
25 layers
15 layers

100

Time (minutes)

Figure 46. Heating profiles of the heat input layers in the

carbon fabric experiment.

Time (minutes)

Figure 47. Heating distribution through the thickness in the

carbon fabric experiment.

The carbon fabric as a heating source offers a good heating performance. Also the
implementation of the heating technique is easy. Moreover, many layers of carbon fabric can be
integrated inside the product,resulting in a hybrid composite.

3.3.6 Combination of carbon fibre and thermofoil

After the tests with all the heating methods described above, it was decided to test a combination
of the fastest and most uniform heating methods. This resulted in the following heating method:
thermofoil at the mould side of the laminate, the carbon fabric as inside heating and the top
infrared panel as the top surface heating. A heating cycle with the dry fibres showed excellent
heat symmetry. As can be seen from the heating profiles during the heating to cure temperature,
see Figure 48, the thermofoil and the carbon fabric heat up faster that the top IR panel. The layer

33

th

slowest in heating up is therefore the 30 layer. To reach 180C, it took approximately 7 minutes.
It can be seen that after those 7 minutes, all the layers in which no heat was supplied showed a
similar exothermal behaviour, resulting in a uniform temperature distribution, which was the
objective of this study.

200
190
180

Temperature (C)

170
160
Top

150

30

140

25
Middle

130

15
10

120

Bottom

110
100
0

10

12

14

16

Time (min)

Figure 48. Heating profiles through the thickness of the laminate during heating from 110 to 180C with a resistive carbon
fabric in the middle of the fibre lay-up and the infrared heating as surface heating

3.4 Comparison of heating methods

3.4.1 Heating rate
The heating rates that were obtained during the experiments for the slowest heated layers are
summarized in Table 7. It can be seen that a few heating methods that were tested comply to the
required heating rate needed for the isothermal infusion strategy being researched; namely the
thermofoil with the top infrared panel, the carbon fabric in combination with the infrared panels
and the final combination of thermofoil, carbon fabric and the top infrared panel.
Table 7. Comparison of heating rate of different heating methods

Heating method
Slowest layer Max heating rate(C/min.) To 180(min.)
Heated platen
Middle
11
13,5
IR top + bottom
Middle
6
12,0
Thermofoil + top IR
Middle
11
7,0
Resistive
10
18
10,0
Carbon fabric
10
16
7,0
Thermofoil + Carbon fabric + top IR
30
19
7,0

3.4.2 Heat distribution

Three possible heating methods were selected from the heating rate of the whole laminate.
However, not only the heating rate is of importance, also the heat distribution through the
thickness. Therefore, the temperature results through the thickness of the laminate that were
obtained right before the polymerzation reaction started are shown in Figure 49. The heating
method with the thermofoil, carbon fabric and infrared panel proofed to have the most unifrom

34

heat distribution. The heating method with the carbon fabric also shows a heat distribution that is
within the limits of what is needed for the process (5C).
45
40
35
30
Thermofoil+Carbon+IR

Layer

25

Carbon+IR

20

Resistive+IR

15

Thermofoil+Top IR
Platen press

10
5
0
-5
135

145

155

165

175

185

Temperature (C)

Figure 49. Heat distribution for different heating methods, before start of the chemical reaction

3.5 Conclusions
For the isothermal infusion of thick laminates, different heating methods were tested. It was
shown that for obtaining a sufficiently high heating rate (from 110 to 180C in 8-10 minutes) only
one type of surface heating of the mould gave adequate results, namely thermofoil, which has a
high heat transfer in combination with infrared. The other possible heating methods had a heating
source in the middle of the laminate: namely a carbon fabric that was used as a resistive heating
source. This technique was used in combination with the double infrared panels or with the
thermofoil and infrared panel. As a uniform heat distribution is wanted as well for the uniformity of
the laminate properties through the thickness of the laminate, it was clear that that goal was only
reached if heating from the inside was applied.
However, these resistive heating sources, as researched in this chapter, need connections for the
power supply which are not easily adapted for the heating of large wind turbine blades. It is
therefore advised to investigate the potential of induction heating. Induction heating is the heating
process of a metal or conductive object by electromagnetic induction, where eddy currents are
generated within the metal resulting in resistance heating of the metal. Because no contact is
needed to heat a piece of metal, this would be an ideal technique to heat metal objects inside a
laminate, thus heating from the inside. The basic components that are needed are an AC power
supply, induction coil and the material to be heated. Another heating source that might be worth
researching is microwave heating. This microwave technology is also an inside out heating
method.
From a mould point of view, several conclusions could be drawn when heating with infrared.
Painting the Al mould plate with a mat black paint increases the radiation absorption. An
aluminium mould is preferred over a Steel one as its thermal diffusivity is higher. And the
thickness of the mould plate is also important, a thinner plate needs less energy to heat up itself
and can therefore transport heat quicker. However, the stiffness of the mould is also important for
the final product.

35

4 Reduction of cure shrinkage induced voids

4.1 Introduction
As could be concluded from the work described in section 2.4.2., voids have a great influence on
the mechanical properties of the composite. Three types of voids can be distinguished:
Mechanical air entrapment during flow in fibre reinforcement
Gas diffusion into reactive resin mixture
Resin shrinkage upon solidification
In section 2.4.2., the reduction of voids due to gas diffusion and mechanical air entrapment during
the flow were described. However, the pure APA-6 resin also exhibits high levels of shrinkage (up
to 9% in volume) and therefore shrinkage induced voids are one of the issues for the composites.
To counteract this shrinkage, a rubber-toughened activator (R) is suggested.
In [30], the material requirements for wind turbine blades are described as followed: the material
needs to exhibit a high material stiffness, a low density and a long fatigue life, also the material
fracture toughness is of importance. The addition of rubber to the material system will soften the
matrix material, and will therefore render the material more fatigue resistant which is one of the
key requirements for large-scale wind turbines. From literature, it can be expected that the use of
activator R will improve the impact properties due to the rubber content. A trade-off between a
loss in stiffness and improvement in fatigue properties needs to be made. Therefore, an
optimization of the amount of rubber that is required in the composites needs to be performed as
well as a comparison between the system that currently has been researched (activator C).

4.2 Experimental
4.2.1 Materials
For the research on the rubber toughened activator, the baseline material had the same
constitution as described in section 2.2.1. For the rubber toughened activator, a liquid activator,
activator R was used in different concentrations, as will be described in this chapter. This
activator was used in combination with initiator M, in the same concentration as previous
research namely 1.2% mol. All the components were supplied by Brggemann Chemicals,
Germany.

4.2.2 Processing methods

The processing methods for the preparation of the resin and the infusion of the laminates are the
same as described in section 2.2.2.
Infusion of pure resin panels
The manufacturing of the 3 mm thick pure resin panel was done at Bruggemann Chemicals using
an injection machine. The mould temperature was set to 160C while the MMU was used at
110C. After 45 min of cure, the panel was removed from the mould and was cooled down to
room temperature.

4.2.3 Analysis methods

The viscosity measurements and the test for the determination of the degree of conversion are
the same as described in section 2.2.3.
Reactivity tests
Glass test tubes with a diameter of 20mm and a length of 150 mm (Schott-Fiolax) were used to
make pure resin samples. The first one, tube A, is filled with a solution of activator/monomer and

36

the second one, tube B, with a solution of initiator/monomer. The test tubes are then put into a
preheated silicon oil bath at 160C. The resin in t he test tubes is stirred regularly and its
temperature is monitored. When both solutions reach 120 C, solution B is poured down into the
tube A. The mixture is then stirred and the tube is placed back in the silicon bath. From then on,
three times are recorded. The first (t1) is when the solution becomes viscous, which is a measure
for the infusion window of the resin, the second (t2) when the solution becomes turbid, which is a
measure for the start of the polymerization. And finally, the time at which the polymer formed
comes loose from the test tube wall (t3), which is a measure for the time to crystallisation. Any
special features observed will also be reported.
Degree of crystallinity
The degree of crystallinity (Xc), the melting temperature (Tm) and the cold crystallisation
temperature (Tcc) of the polymer are determined by means of a Perkin Elmer Differential
Scanning Calorimeter (DSC). Disc-shaped samples (msp) of approximately 5 mg are taken from
the laminate at the same location as the degree of conversion samples and are dried overnight.
In the DSC, the test sample is held at 25C for two minutes and is then heated up to 240C at a
rate of 10C per minute, where they are held for tw o minutes. After that, they are cooled down to
room temperature at a rate of -10C per minute. The results had to be corrected for the fibre and
rubber content of the sample. The degree of crystallinity can now be calculated as follows:

Xc =

H m
mtotal

100
H100 mtotal m fibres mrubber mmon

(4)

Density
ASTM Standard D792-00, Test Method A, was used to calculate the density of the material. To
determine the practical density of the specimen, the specimen was first weighed in air (msp) on
the AG204 DeltaRange balance. Next, the specimen had to be fully submersed in water. The
temperature of the water was measured, from which the density of the water could be calculated
and a wire assembly was connected to the balance and suspended in water. After that, the
specimen was attached to the wire, suspended in water and measured (msp,water). The density of
the specimen could then be calculated as follows:
(5)

pract =

(m

water

sp

sp

msp , water )

Tensile testing
The tensile properties of the pure resin were measured by means of the ISO-527-1 Standard,
with dogbone shaped specimens that had a thickness of 3 mm. The test specimens were milled
out of the flat plate and dried before testing for at least 48hours at 50C under full vacuum. At least
five samples were tested per panel on a Zwick 20kN static test machine.
Impact resistance
The impact resistance of pure resin samples were tested by means of an Izod test, ASTM D25605a. The notched specimens were milled according to the standard Test Method A and had a
thickness of 3 mm. The type of failure was noted and the energy to break was measured for each
specimen and from that, the impact resistance of the specimens could be calculated. At least, five
specimens were tested per panel. The samples that were tested were either dried at least 48
hours at 50C under full vacuum, or conditioned up to the equilibrium water uptake in a climate
chamber at 70C and 62%RH, according to ISO1110 Sta ndard.
Moisture uptake
Samples were conditioned in a climate chamber at 70C and 62%RH until the equilibrium
moisture uptake was reached. Then the samples were mechanically tested.

37

4.3 Resin constitution

The potential advantages of activator R for the APA-6 composites need to be investigated.
Therefore, the amount of the rubber content and the initiator needs to be found by means of
reactivity tests and viscosity measurements.
First of all, it needs to be checked whether the resin reacts well, gives enough time to infuse the
composites, and see the effect on shrinkage time. Therefore, reactivity tests were performed at
different levels of initiator and activator. A rubber content of 7% and a 1.2%mol concentration of
the initiator gives the best compromise for the vacuum infusion system, (as can be seen in Figure
50):
Biggest infusion window
Highest time to polymerize (enough time to heat laminate before reaction starts)
Average time to shrink. After polymerization, the polymer chains needs to react with the
fibre sizing as well, therefore enough time between polymerization and crystallization is
needed.
40
30

T1
T2
T3

25

C-M system

Time [min]

35

20
t3

15
10

t2
t1

5
0
0

10

15

20

25

Amount of rubber [%wt]

Figure 50. Reactivity of the resin with different amounts of rubber. T1 stands for the infusion window, T2 for the start of the
polymerisation and T3 for the start of the crystallisation. The system has been compared to the reaction times of the
normal system.

With increasing amount of activator R, the mixture becomes more reactive, therefore, the time to
polymerize decreases. As the rubber content complicates the crystallization the time to crystallize
increases with increasing amount of rubber. When compared to the activator C system, it can be
concluded that the time difference between t1 and t2 is significantly higher. It is therefore needed
to check the reaction rate of the system by means of viscosity measurements.
1,200

viscosity (Pa.s)

1,000
0,800
C-M 180
C-M 170

0,600

C-M 160
R 7% 160

0,400

R 7% 170
R 7% 180

0,200

19:5

19:1

18:4

18:0

17:3

16:5

16:2

15:4

15:1

14:3

14:0

13:2

12:5

12:1

10:3

8:45

7:00

5:15

3:30

1:45

0:00

0,000

time (min)

Figure 51. Viscosity versus time for different material systems: C-M and R-M at different testing temperatures: 160-170
and 180C

As can be seen in Figure 51, the effect of the testing temperature is the same for activator C and
R. The higher the testing temperature, the faster the reaction starts and the higher the reaction
rate. It can also be seen that for the optimal resin constitution of 7%wt of activator R, the reaction
starts significantly later than when compared with the activator C. Also, the reaction rate is lower.
Using the activator R slows down the start of the reaction, as the amount of reactive parts in the

38

mixture is lower that with the mixture with activator C. The equivalent amount of activator R
needed to have the same amount of reactive groups is 24.15%. Viscosity measurements were
done for activator R concentrations of 7-10-15-20-24.15%wt at three testing temperatures: 160170-180C. In Figure 52, a summary of the results is shown for a testing temperature at 160C.
By increasing the rubber content in the resin, the reaction rate and initiation of the reaction
increases significantly due to addition of the reactive groups. Although, the reaction rate is still
lower than with the activator C system. It can also be seen that the initial viscosity of the resin, at
the beginning of the test, is higher than with the normal system. This might be disadvantageous
for the infusion, as a low viscosity is wanted.
1,200
C-M 160

viscosity (Pa.s)

1,000

R 20% 160
R 7% 160

0,800
0,600
0,400
0,200

19:50

19:15

18:40

18:05

17:30

16:55

16:20

15:45

15:10

14:35

14:00

13:25

12:50

12:15

8:45

10:30

7:00

5:15

3:30

1:45

0:00

0,000

time (min)

Figure 52. Viscosity versus time for different material systems: R-M at7% and 20%wt and C-M. at a testing temperature of
160C

The value of 1 Pa.s is seen as the maximum viscosity for vacuum infusion of composites. If a look
is given to Table x, it can be seen with low rubber contents in the resin, the infusion window is
long. Increasing the rubber content does not seem to reduce the infusion window as significantly
from a rubber content of 15% on. Also the reaction rate is comparable for the tests done for a
rubber content of 15, 20 and 24.15%wt.
Table 8. Infusion window for different material systems: C-M and R-M at different amount of R at different testing
temperatures

Time to 1 Pa.s (min)

160C
170C
180C

C
12,35
10,22
5,2

7%
20,02
15,8
12,44

10%
15
10,83
9,9

15%
12,32
9,3
7,87

20%
15,83
9,76
8,43

24,15%
9,39
8,25

It can be concluded from these results that the activator R seems a suitable candidate for infusion
of large composites, due to its long infusion window and its acceptable reaction rate.

4.4 Pure resin

To investigate the behaviour of the pure resin, 3mm thick panels were manufactured with different
amounts of rubber: 7-10-15-20%wt activator R. Two panels per activator concentration were
infused. Also, two baseline panels with the C-M formulation were made for comparison Those
panels were tested for degree of conversion, degree of crystallinity, cold crystallization, tensile
properties, water uptake and impact properties.
It was seen that the degree of conversion of the panels with activator are comparable with the
normal system and that there is no difference in degree of conversion when the rubber content is
increased. Therefore, it can be concluded that the degree of conversion is not a significant factor
in the interpretation of the results.

39

50,00
48,00
46,00
44,00
Xc

42,00
40,00
38,00
36,00
34,00
32,00
30,00
Cx

S-7

S-101

S-15

S-20

Figure 53. Degree of crystallinity for the normal C-M

system and for different amounts of rubber in the R-M
system.

For the degree of crystallinity, it can be seen that the standard deviation is high for all the test
samples, see Figure 53. Although no trend can be seen with increasing rubber content, a
significant increase in degree of crystallinity can be seen when the activator R system is
compared to the normal system. The increase in crystallinity with activator R can be explained
due to the fact that more mobile chains align more easily to form crystals. To verify this, the
enthalpy during the cold crystallization (crystallization from the melt) was studied in the DSC. With
activator C, more energy was generated for the formation of the crystals. A clear decrease in
crystallization enthalpy (Figure 54) and cold crystallization temperature (Figure 55) can be seen
with increasing rubber content. Up to 15%, the polymer with activator R crystallises faster, more
easily, at higher temperature than with activator C. The increase of rubber above 15%wt shows
that a more difficult crystallization behaviour, as a more cross-linked polymer system is obtained.
Therefore it becomes more difficult to crystallize and more supercooling is needed to form
crystals in the structure, hence a lower Tcc.
179

58

178

Peak temperature (C)

56

Enthalpy (J/g)

54
52
50
48
46
44

177
176
175
174
173
172
171
170
169

42

40
0

10

15

20

25

10

15

20

25

Percentage of activator R

percentage of activator R

Figure 54. Enthalpy of cold crystallisation for the normal C-M

system and for different amounts of rubber in the R-M system.

Figure 55. Peak temperature of cold crystallisation for

the normal C-M system and for different amounts of
rubber in the R-M system.

For the mechanical properties, the tensile and impact properties were measured. For which the
results are shown in Figure 56 and Figure 57 respectively. Activator C clearly exhibits better
tensile properties due to the higher stiffness of the chains. The more activator R is added to the
system, the lower the stiffness. As the crystallinity increases by using the rubber-toughened
activator, a higher E-modulus is expected when compared to the normal system. However, by
using rubber, more flexible parts are added in the polymer chains and therefore the E-modulus
will decrease, as can be seen in the graph.
A lower impact resistance is seen for the activator R panels when compared to the activator C
system. The higher amount of crystallinity of the P5 polymer might render it more brittle on impact.
All the specimens exhibited a complete break, showing a brittle-like behaviour. Increasing the
amount of activator R, lowers the impact resistance up to 15%. Increasing the rubber content to
20% increases the impact resistance again. The decrease in impact resistance can be attributed

40

to a more cross-linked system. Again, at around 15% of rubber, a transition point from a reaction
point of view is seen.
3000

35
DRY
Impact resistance [J/m]

E modulus [MPa]

2500

2000

1500

1000

500

30
25
20
15
10
5

0
C

10

15

20

Figure 56. E-modulus for the normal C-M system and for
different amounts of rubber in the R-M system.

0
C
7
10
15
20
Figure 57. Dry impact resistance for the normal C-M system
and for different amounts of rubber in the R-M system.

While in the dry state, the activator C outperforms the R system in impact resistance, the rubber
toughened system takes over in a conditioned state, see Figure 58. The impact resistance results
are increased with a minimum factor of 8. The high increases with 7 and 10%wt of rubber can be
attributed to a incomplete break (increase with a factor of min. 31) which can be attributed by their
higher equilibrium water uptake level. The transition in the material is seen at 15% from
incomplete break to a hinge break.
It was also seen that the cure time of the samples has a significant effect on the impact
resistance see Figure 59. For a shorter cure time, a higher impact resistance was found due to a
less entangled system upon curing, therefore lowering the impact resistance.
DRY

Impact resistance [J/m]

800

WET

700
600
500
400
300
200
100

Impact resistance [J/m]

900

1000
800
600

30 min dry
45 min dry

400

30 min wet

200

45 min wet

0
7

0
C

10

15

10

20

Figure 58. Dry and conditioned impact resistance

for the normal C-M system and for different
amounts of rubber in the R-M system.

Figure 59. The impact resistance for specimens cured at

30 or 45 min, in dry or conditioned state, for 7 and 10%
of rubber in the R-M system.

As could be concluded from the research on the pure resin, the rubber toughened system shows
a lot of potential for the use in production of laminates. The resin reacts nicely at all rubber
contents tested and shows a higher crystallinity than the normal system. A loss of stiffness was
found, while the impact resistance and material toughness increases when the samples are
conditioned.

4.5 Laminates
Now that the behaviour of the pure resin is known, laminates can be produced and tested. After
that, the properties like degree of conversion, degree of crystallinity can be tested to see whether
the same trends as for the pure resin can be found. A comparison can be made with the normal
system. Only preliminary results can be shown in this section. Panels with different amounts of

41

96,0%

98%

95,5%

97%

95,0%

96%
DOC (%)

DOC (%)

activator R (10, 15 and 20%wt) were infused with infusion strategy 1. Also different cure
temperatures were tested for the rubber content of 15%. All panels reacted as expected, but due
to a change in the chemicals and infusion behaviour, the results that are shown are not yet
repetitive. The laminates have therefore not been tested mechanically yet.

94,5%
94,0%
93,5%

95%
94%
93%

93,0%

92%

92,5%

91%

92,0%
155

160

165

170
175
Temperature (C)

180

185

Figure 60. The degree of conversion for laminates with

15%wt rubber at different processing temperatures.

10
15
20
concentration of activator R (%)

25

Figure 61. The degree of conversion for laminates

manufactured at 180C, with different amounts of rubber.

As can be seen from both Figure 60 and Figure 61, the values for the degree of conversion of the
laminates are lower than for the pure resin. The addition of the fibres is known to affect the
conversion negatively, as seen in the work of van Rijswijk. As was seen from this work, the
decrease in degree of conversion (Figure 60) and in degree of crystallinity (Figure 62) with
increasing processing temperature is as expected. The value of the degree of conversion at
170C shows a high standard deviation due to a bad quality of the laminate, which was a
production error. What can be seen from Figure 61 is that the degree of conversion increases
with the increase of concentration of activator R. Increasing the amount of rubber at a processing
temperature of 180C, does not show any trend for the degree of crystallinity, due to the high
standard deviation. All the values for the degree of conversion are still in the acceptable range for
the laminates. The selection of the best quantity of rubber to be used will thus be dependent on
the mechanical properties of the laminates, which is not part of this work.
38

44,00

37

42,00

36

40,00
Xc

Xc

35
34

38,00
36,00

33
32

34,00

31

32,00

30
155

30,00
160

165

170

175

180

185

Temperature (C)

Figure 62. The degree of crystallinity for laminates with

15%wt rubber.

0%

5%

10%

15%

20%

25%

Concentration of activator R

Figure 63. The degree of crystallinity for laminates

manufactured at 180C, with different amounts of rubber.

4.6 Conclusions
It can be concluded from the results on reactivity that the activator R seems a suitable candidate
for infusion of large composites, due to its long infusion window and its acceptable reaction rate.
As could be concluded from the research on the pure resin, the rubber toughened system shows
a lot of potential for the use in production of laminates. The resin reacts nicely at all rubber
contents tested and shows a higher crystallinity than the normal system. A loss of stiffness was
found, while the impact resistance and material toughness increases when the samples are
conditioned. All the values for the resin properties are in the acceptable range for the laminates.
The selection of the best quantity of rubber to be used will thus be dependent on the mechanical
properties of the laminates, which is not part of this work.

42

5 Optimisation of fibre-to-matrix bond

5.1 Introduction
It could be concluded from the work of van Rijswijk [23] that the fibre-to-matrix bond in
combination with good resin properties is the key parameter to good mechanical properties. An
improvement in fibre-to-matrix bond will result in an increase in fatigue properties and in a better
resistance to moisture absorption. It was also seen that the void content is closely related to the
interface properties; the better the interface, the lower the final void content.
The fibre-to-matrix bond between the APA-6 resin and the glass fibres used to reinforce the
laminates can be improved by using a chemical sizing on the glass fibres that is compatible with
the resin system. It is proven to be difficult to find a compatible sizing for the APA-6 system. To
be able to test the fibre-to-matrix bond strength of different sizing, uni-directional (UD) transverse
tensile tests have proven to give good quantitative results. For this purpose, a method to infuse
UD laminates needs to be developed.
In this chapter the effect of the fibre sizing on the mechanical properties will be described, the
UD-infusion set-up and the optimization thereof. All the fibre rovings that will be tested in this
research are classified as E-glass fibres. They have the same density and their nominal E-moduli
should be around 75GPa. To exclude the differences between the fibres when testing the fibre-tomatrix bond, the E-modulus of the different fibres will be tested, and afterwards the fibre-to-matrix
bond of the UD laminates will be tested.

5.2 Experimental
5.2.1 Materials
The same resin materials were used as described in section 2.2.1.
Glass fibres
Different types of glass fibres were tested in this research, all with different sizings and properties:
P4510, J058, J858, and J870. All the glass fibres that were tested are E-glass fibres. For the
optimization of the infusion process of the UD laminates, the 4510 fibre was used.

5.2.2 Processing methods

The same processing methods were used as described in section 2.2.2. For the infusion strategy
of the UD-laminates, an optimization of the infusion strategy 1 was done.

5.2.3 Analysis methods

Tensile tests
Tensile tests were done on the dry glass fibre rovings and on the UD laminates.
The tensile test of the roving was performed according to the ISO 3341 Standard. The roving was
clamped with a radius clamp to avoid slippage during the test. The gauge length of the fibre with
the radius clamps was set at 300mm. An extensometer was used to measure the elongation of
the specimen. The two parts of the extensometer were placed at a distance of 200 mm to
measure the E-modulus. At least five tests were done with each fibre roving for the determination
of the E-modulus. A tangent method was used to determine the E-modulus. The tests were
performed on a 20kN Zwick static test machine.
The transverse tensile test was used to test the fibre-to-matrix bond in which the specimens are
tested in transverse fibre direction, therefore testing only the fibre-to-matirx bond. The tensile
specimens with a thickness of 2 mm were prepared and tested according to ASTM Standard
D3039. The width and the length of the specimens were 25 and 175 mm respectively. No gripping

43

tabs were applied on specimens. The 20kN Zwick testing machine was used for the tensile test.
The testing speed applied was 2mm/min.
Degree of conversion
The degree of conversion of the UD laminates were measured by means of the same test as
described in section 2.2.3.

5.3 Effect of fibre sizing

The effect of the fibre-to-matrix bond was previously tested by means of the short-beam strength
test. This mechanical test is however also dependent on the resin properties, the mechanical
locking due to resin shrinkage and the chemical bonding. It is difficult to get a good overview of
the real fibre-to-matrix bond via this test method. Therefore, the UD laminates and the transverse
tensile test needs to be tested for its suitability to test the fibre-to-matrix bond.

Interlaminar shear strength [MPa]

80
70
60
50
40
30
20

APA-6 composite (unsized/outlet)

APA-6 composite (sized/outlet)

10
140

150

160

170

180

190

200

Mould temperature [C]

Figure 64. Effect of the fibre sizing of the short-beam strength at different processing temperatures.

From the previous research, it was seen that a drop in short-beam strength could be observed
when using the unsized glass fibres. The drop in short-beam strength can be explained by a poor
fibre-to-matrix bond. With unsized fibres, the chemical bonding of the polymer chains to the glass
fibre surface is not present, which leads to a significant drop in short-beam strength. It can
therefore be concluded that the usage of a fibre sizing as well as unblocked activators (which are
responsible for the adhesion to the fibre sizing) are essential for chemical bonding and good
mechanical properties.

5.4 Characterisation of glass rovings

Force (N)

In Figure 65, the test results of the four types of fibre rovings are shown. As said previously, the
nominal E-modulus for the E glass fibre has to be 75 GPa. To determine the best properties
between fibres tested, there are some characteristics that can be studied, which can be found in
Table 9 . The E-modulus is the most important factor, corresponding to a material with a high
strength with minimal deformation.
1400
1200
1000
800
600
400
200
0

P4510
J058
J858H
J870

0,5

1,5

Strain (mm)
Figure 65. Comparison of the tensile strength of different fibre types

44

From Table 9, it can be concluded that the J870 fibre has the lowest E-modulus due to a different,
rougher texture, as a result of the manipulation in the test set-up. The other three types of fibres
are considered good enough to be used in laminates. In Figure 65, it can be seen that there is no
difference between the other three fibre types when it comes to strain. The J058 fibre shows the
highest maximum force but with a high standard deviation.
Table 9. Comparison of tensile properties of glass fibre rovings

Fibres
E-Modulus (MPa)
Stdev
Max_value (N)
Stdev
Elongation (mm)
stdev

P4510
73930
5068
598
80,7
0,874
0,150

J058
75841
5966
1108
212
0,835
0,207

J858
74237
5633
518
29,2
0,802
0,108

J870
31365
5639
502
49,0
1,78
0,173

5.5 Vacuum infusion set-up for UD laminates

For the production of UD laminates, the dry fibre rovings are first uni-directionally filament wound
2
around an Al mould. The mould used is a supporting Al plate (45x45cm with a thickness of 2 mm)
to which two levers can be connected for the filament winding process, see Figure 66. The fibres
are wound around the mould in four layers, see Figure 67, which will give a final thickness of the
laminate of 2 mm after cure, as required by the test method. The width of the laminate will be 20
cm.

Figure 66. Al supporting plate (for both winding and

infusion)

Figure 67. Dry filament wound fibres around Al supporting

plate

After the winding process, the vacuum bagging can begin and is done as with the normal
laminates, as described in section 2.2.2. The tacky tape is placed around the mould on both sides
of the mould. Then, the inlet and outlet springs and tubes are connected, as can be seen in
Figure 68. The type, size and placement of the inlet and outlet were changed in the optimization
process. It turned out that when the inlet or outlet spring were connected to an aluminium tube
which is placed on the edge of aluminium supporting plate gives the best connection. Thin Al
cover plates with a thickness of 2 mm were used to improve the surface quality (Figure 69) and a
more uniform thickness.

45

Figure 68. Tacky-tape applied and in- and outlet connected

to the mould set-up

Figure 69. Al covering plates placed on the fibres for better

surface quality

Finally, the bagging could be finished by applying the polyimide foil as a vacuum bag and is now
ready to be infused (see Figure 70). The process of the vacuum infusion of UD laminnate has
been already described as infusion strategy 1 in Section 2.2.2. The values of the infusion
parameters are summarized in Table 10. However, because of complexity of UD laminates
vacuum infusion, the process parameters like polymerization temperature, temperature in MMU
and in the resin buffer, the infusion pressure and polymerization time were variable.

Figure 70. Fully vacuum bagged mould ready for infusion

Figure 71. A fully cured UD laminate.

As it turned out that it was difficult to fully impregnate the fibres, the infusion parameters stated
above were optimized. When a glass fibre fabric is used in the infusion process, the infusion of
the resin takes place uniformly due to the fibres that are not only orientated in flow direction but
also in transverse direction. Therefore the flow is restricted during infusion but the resin is
distributed over the complete surface. For the infusion of UD laminates, there are only fibres in
flow direction. The resin will always flow along the easiest path, for example where the density of
winded fibres is lower. Therefore, the infusion process will be more susceptible to nonuniformities resulting in non-impregnated areas in the final product.
Table 10. Infusion parameters for the UD infusion process, for different type of tests

Start values
Test 1
Test 2
Test 3

MMU & buffer

vessel
110C
100C
100C
100C

Preheated
glass fibres
180C
180C
160C
180C

Cure
temperature
180C
180C
180C
180C

Infusion
pressure
250 mbar
140-150 mbar
100 mbar
140-150 mbar

Flow length
45 cm
45 cm
45 cm
30 cm

46

The infusion parameters used for the first infusion were the start values stated in Table 10. The
infusion the UD laminate was not complete. It was thought that the reaction mixture was not able
to reach the outlet before viscosity got increased due to fast polymerization and the mixture
stopped flowing. It was therefore thought that reducing the infusion pressure, lowering the
temperature of the preheated glass fibres and lowering the temperature of the MMU and the
buffer vessel, would allow the laminates to be fully impregnated. The tested infusion parameters
are summarized as Test 1 and 2. Although good and nicely polymerized products were obtained,
still some dry spots were observed near the outlet of the product. To check whether the problem
of filling the complete product was related to the infusion length, tests were done with a smaller
plate, 30 cm long instead of 45cm. The infusion parameters were similar to Test 1. At these
conditions, the UD laminates were fully impregnated and nicely cured.
Compared to the tests done with these parameters with a longer flow length, it can be concluded
that a lower flow length gives better results. During infusion, the inlet is clamped off at the
moment that the resin stopped flowing. Therefore, more resin can flow through the shorter UD
laminates, allowing the product to be fully impregnated before the resin stops flowing due to the
polymerization reaction. In order to fully impregnate UD laminates with longer lengths, infusion
strategy 2, as described in section 2.2.2. , would be a possible solution as the resin and the fibres
are at a lower infusion temperature, allowing the resin to flow without a fast reaction. However,
the effect of the second infusion strategy on the fibre-to-matrix bond needs to be tested first and
will be part of future work. It is however of utmost importance that the reaction kinetics as studied
in section 2.3. are implemented in a flow simulation program in order to select the best infusion
parameters and strategy.

5.6 Characterisation of the UD-laminates

Degree of conversion
To determine whether the procedure of UD laminates vacuum infusion provides products with a
high polymer yield in matrix, the optimized panels were tested for degree of conversion. An
average value of 97.4% was found with a low standard deviation of 0.26. All the laminates have a
high polymer yield (DOC). It could also be concluded that the use of different proccess
parameters did not affect the final quality of UD laminates polymer matrix at least in terms of
polymer yield.
Tensile tests
To check whether the UD laminates are useful for determination of the fibre-matrix bond strength,
laminates were tested in a transverse tensile test as described in section 5.2.3. The transverse
tensile results for the different tests that were described in section 5.5, Table 10, are shown in
Figure 72. As can be seen, the infusion parameters as used in Test 1 and 3 turn out to give the
best values. For Test 2, there was only one laminate that was tested, hence no standard
deviation of the process could be given. From the standard deviation of Tests 1 and 3, it can be
concluded that the process is quite repeatable. The shorter the flow length, the higher the fibre-tomatrix bond, as is expected due to the better impregnation of the fibres, as described in section
5.5.
One laminate that was infused with the setting of Test 3, was tested for both sides of the infusion.
The results for the lower and upper part (during infusion) of the panel are represented in Figure
73. A better bond strength is found for the lower part during the infusion. Due to gravity, more
resin will flow through the bottom side of the laminate during infusion. Hence, that part is better
impregnated, increasing the fibre-to-matrix bond. It can therefore be concluded that the
transverse tensile test is able to quantify the fibre-to-matrix bond. Further research can now focus
on the comparison between different fibre sizings and the effect on the fibre-to-matrix bond as
well as on the change in infusion parameters and its effect on the interface bond strength. For the
next experiments, it is advised to use tabs for more consistent measured data.

47

Average maximum strength [MPa]

A verag e m axim um stren gth

[M Pa]

16
14
12
10
8
6
4
2
0

16
14
12
10
8
6
4
2
0
upper

lower

Tests

Figure 72. Average maximum transverse tensile strength of

UD laminates for different infusion parameters

Figure 73. Average maximum transverse tensile strength of

.the upper and lower part of the obtained UD laminate after
infusion

5.7 Conclusions
A set-up for manufacturing uni-directional (UD) laminates has been made and tested. The
infusion process for the UD laminates infusion proved to be more difficult than in the case of
laminates containing glass fibre fabric. The glass fibre fabric has fibres that are not only
orientated in flow direction. This allows for a uniform, restricted flow pattern. For the infusion of
UD laminates, only fibres in flow direction are present. As the resin will always flow along the
easiest path, the infusion process will be more susceptible to non-uniformities resulting in nonimpregnated areas in the final product.
An optimization of the infusion process was done and repeatable results were obtained by
reducing the infusion pressure and decreasing the temperature of the MMU and the buffer vessel.
Al cover plates were used on the fibres to improve the surface quality. It also turned out that the
flow length is a critical parameter for the full infusion of the laminates. For the full impregnation of
longer UD laminates, it would be a possible solution to use infusion strategy 2, as the resin and
the fibres are at a lower infusion temperature, allowing the resin to flow without the fast reaction
reducing the flow velocity. The characterisation of the reaction kinetics of the resin will aid in the
understanding of the infusion process.
It could be concluded from the transverse tensile test results of the UD-laminates that the fibre-tomatrix bond can be quantified. Further research will focus on the comparison between different
fibre sizings and the effect of different infusion parameters on the fibre-to-matrix bond.

48

6 Conclusions and recommendations

6.1 Conclusions
From previous research, a number of questions needed to be answered before the APA-6 system
could be used for the production of large wind turbine blades: the gradient in flow direction and
through the thickness of the laminates needed to be minimized; the fibre-to-matrix bond needed
to be optimized for the optimization of the dynamic properties and durability; an investigation on
the effect of flow length on the properties of the laminates was needed; a reduction of the void
content needed to be investigated and the most significant process parameters needed to be
identified.
For the reduction of the gradient in flow direction, thin glass fibre reinforced APA-6 composites
were researched. To increase the homogeneity of the composites (thermally and chemically) in
flow direction, an isothermal infusion strategy was implemented for the high temperature vacuum
infusion process. Research was focused on the infusion temperature. It was seen that at all
infusion temperatures, a flow gradient was still present. A trade-off needed to be made between
low filtering (low infusion temperatures) and high mechanical properties (higher infusion
temperatures). To further increase the homogeneity, the flow induced gradient was researched. A
high infusion velocity caused a lower gradient in flow direction, but resulted in a lower overall
quality compared to the lower infusion velocity. Applying a post-fill pressure after infusion proofed
to reduce the void content and therefore increasing the mechanical properties and reducing the
flow induced gradient. Flushing the laminate with extra resin during the heating up phase in the
infusion process resulted in a laminate with a significant reduction, or even disappearance of the
flow gradient. To increase the homogeneity of the properties through the thickness of the
laminates, different heating methods were tested. For the isothermal infusion of thick laminates, it
was shown that for obtaining a sufficiently high heating rate (from 110 to 180C in 8-10 minutes)
with a uniform heat distribution throughout the thickness of the laminate, a heating source in the
middle of the laminate was needed in combination with a surface heating of the mould by either
contact or radiation heat.
For the quantification of the fibre-to-matrix bond of the APA-6 composites, uni-directional (UD)
were infused and mechanically tested under transverse tensile load. The set-up for the production
of the UD laminates was designed and tested. After an optimization of the infusion process,
repeatable results were obtained for the UD laminates. It could be concluded from the transverse
tensile test results of the UD-laminates that the fibre-to-matrix bond can be quantified, simplifying
the optimization of the mechanical properties, by varying several process parameters,
significantly in the future.
The effect of increasing the flow length of the infusion was tested. It was seen that there was a
linear increase of infusion time with flow length. All laminates were fully infused without changing
the processing parameters and resulted in good quality laminates. It can therefore be concluded
that the up-scaling of the laminates is feasible.
By investigating the flow parameters during infusion and curing of the APA-6 composites, it was
seen that the void content could be reduced by implementing a degassing procedure, as well as
using a high post-fill process. However, to reduce the voids that occur during the cure and
shrinkage of the resin, a rubber toughened activator was tested. It can be concluded that the
activator R seems a suitable candidate for infusion of large composites, due to its long infusion
window. The resin reacts nicely at all rubber contents tested and showed a higher crystallinity
than the normal system. A loss of stiffness was found, while the impact resistance and material
toughness increases when the samples are conditioned, as expected. All the values for the resin
properties are in the acceptable range for the laminates. The selection of the best quantity of
rubber to be used will be dependent on the mechanical properties of the laminates.

49

It was already shown that the temperature is the most significant parameter of the process. The
effect of the pot life (time and temperature) on the reaction of the resin as well as on the increase
of the viscosity was also investigated. It could be concluded that the pot life will have a significant
effect on the infusion window and the final properties of the laminate. Therefore the pot life is
identified as one of the main parameters for the infusion of large wind turbine blades and needs
further investigation. The effect of the parameters was discussed in the paragraph on the
reduction of the flow gradient. After researching the infusion parameters, the effect of cure and
the post-process was investigated. For the research on the cure parameters, it was seen that the
optimum in mechanical properties and resin properties was found at a cure time of 90 minutes.
The results for the study on the annealing cycle showed that the changes in resin and mechanical
properties were mainly related to the annealing temperature. The biggest improvement was seen
near the crystallization temperature of APA-6 (175C), for the laminates that were first cured for
30 minutes. It could be concluded that the selection of the long cure time is most effective for
obtaining good mechanical properties. The same properties could be obtained with an annealing
cycle, although requiring more time in the mould and more heating energy.

6.2 Recommendations
For increasing the homogeneity in flow direction of the laminates, a low infusion temperature is
required. However, due to the low heating rate of the heating method used in this study, the
mechanical properties were low. It is recommended to investigate the effect of the heating rate on
the composite properties. It is expected that if the heating rate can be increased the optimum
mechanical properties might be found at the same low infusion temperature, where lower filtering
was observed. It is also thought that the flow induced gradient might be reduced by flushing the
laminate with extra resin after the wet-out of the fibre preform.
Investigating the effect of this residence time or pot life more fundamentally by means of reaction
kinetics is seen as a critical part in the investigation on the infusion of large wind turbine blades. A
long residence time or pot life is needed to infuse these products without compromising the resin
properties. It is therefore thought that tests on the reaction kinetics of the resin will help in the
understanding of the reaction and the effect of the residence time and temperature on the
reaction. Initial tests were performed and setting the semi-empirical equations for the simulation
of the resin reaction has been started. If this behaviour is characterized, and are implemented in
a flow simulation program, an optimal infusion strategy can be chosen for the infusion of the large
composite products.
For increasing the homogeneity through the thickness of an isothermally infused thick-walled
laminate, it was shown that heating from the inside was needed. However, the resistive heating
sources as testes in this research, needed connections for the power supply which are not easily
adapted for the heating of large wind turbine blades. It is therefore advised to investigate the
potential of induction heating. Induction heating is the heating process of a metal or conductive
object by electromagnetic induction, where no contact between the power supply and the
resistive medium is needed. Another heating source that might be worth researching is
microwave heating. This microwave technology is also an inside out heating method.
A rubber toughened activator was tested to reduce the voids that occur due to shrinkage of the
resin. The addition of rubber to the material system will soften the matrix material, and will
therefore render the material more fatigue resistant which is one of the key requirements for
large-scale wind turbines. During the research, it was shown that this resin shows a lot of
potential. However, the use of this activator for the laminates was not tested yet. The selection of
the best quantity of rubber to be used will be dependent on the mechanical properties of the
laminates. The effect of the activator on the shrinkage and void content reduction needs to be
tested as well.
For the quantification of the fibre-to-matrix bond, UD laminates were infused and mechanically
tested under transverse tensile load. Further research will focus on the comparison between

50

different fibre sizings and the effect of different infusion parameters on the fibre-to-matrix bond. A
further optimization of the infusion process for the UD laminates will be performed as well.

51

References
1.
2.
3.

4.

5.

6.

7.

8.
9.
10.

11.

12.
13.

14.

15.

16.
17.
18.

19.
20.

th

Cano R.J., High temperature VARTM with LaRC polyimides, In 36 International

SAMPE Technical Conference; San Diego, CA, 2004
Bower M.V., Composite Materials, University of Alabama, Huntsville, Alabama, 2000
Pillay S., Vaidya U.K. and Janowski G.M., Liquid moulding of carbon fabric-reinforced
nylon matrix composite laminates, Journal of Thermoplastic Composite Materials, Vol.
18, 2005, pp. 509-527.
van Rijswijk, K., Thermoplastic Composite Wind Turbine Blades Vacuum Infusion
Technology for Anionic Polyamide-6 Composites, Ph.D. Dissertation, Delft University of
Technology, 2007.
van Rijswijk K., Bersee H.E.N., Jager W.F., Picken S.J. Optimisation of Anionic
Polyamide-6 for Vacuum Infusion of Thermoplastic Composites: Choice of Activator and
Initiator, Composites Part A: Applied Science and Manufacturing, Vol. 37, 2005, pp 949956.
Ueda K., Hosoda M., Madsuda T., and Tai K. Synthesis of high molecular weight nylon 6
by anionic polymerization of -caprolactam. Formation of cyclic oligomers, Polymer
Journal, Vol. 30, No. 3, 1998, pp. 186-191.
Cartledge H. and Baillie C.A. Study of microstructural and mechnical properties of
nylon/glass composite. Part i. The effect of thermal processing on crystallinity,
transcrystallinity and crystal phases, Journal of Materials Science, Vol. 34, No. 20, 1999,
pp 5099-5111.
van Geenen A.A. Anionic polyamide 6 chemistry and processing. Internal report, DSM
Plastics, 2002.
van der Vegt A.K. From Polymers to Plastics. DUP Blue Print, 2002.
van Rijswijk, K., Bersee H.E.N., Beukers A., Picken S.J., van Geenen A.A., Optimisation
of anionic polyamide-6 for vacuum infusion of thermoplastic composites: Influence of
polymerization temperature on matrix properties, Polymer testing, Vol. 25, 2006, pp.
392-404.
van Rijswijk K., Lindstedt S., Vlasveld D.P.N., Bersee H.E.N., Beukers A. Reactive
processing of anionic polyamide-6 for application in fiber composites: a comparative
study with melt processed polyamides and nanocomposites, Polymer testing, Vol. 25,
2006, pp. 873-887.
Wicks Z.W., Blocked isocyanates, Process in Organic Coatings, Vol. 3, 1975, pp. 73-99
van Rijswijk K., Teuwen J.J.E., Bersee H.E.N. and Beukers A. The interface of reactiveand melt processed polyamide-6 composites, In proceedings of the 16th International
Conference on Composite Materials, 2007.
Teuwen J.J.E., Gillis J.H.A.M. and Bersee H.E.N. Optimisation of infusion temperature
for anionic polyamide-6 composites. 49th AIAA/ASME/ASCE/AHS/ASC Structures,
Structural Dynamics, and Materials Conference, 2008.
Teuwen J.J.E., van Rijswijk K., Bersee H.E.N. and Beukers A. Effect of fibre textile
reinforcement on anionic polyamide-6 composite properties, In proceedings of the 16th
International Conference on Composite Materials, 2007.
Ghiorse S.R. Effect of Void Content on the Mechanical Properties of Carbon/Epoxy
Laminates. SAMPE Quarterly, 1992
Judd N.C.W. and Wright W.W. Voids and their Effect s on the Mechanical Properties of
Composites an Appraisal. Sampe J, Vol. 14, No. 1, pp 10-14, 1978
Zingraff L., Michaud V., Bourban P.-E., and Mnson J.-A.E. Resin Transfer Moudling of
Anionically Polymerised Polyamide 12. Composites Part A: Applied Science and
Manufacturing, Vol. 36, pp. 1675-1686, 2005
Tackitt K.D., Walsh S.M. Experimental study of thickness gradient formation in the
VARTM process. Materials and Manufacturing Processes, Vol. 20, pp. 607-627, 2005.
Barraza H.J., Hamidi Y.K., Aktas L., ORear E.A., Altan M.C., Porosity reduction in the
high-speed processing of glass-fiber composites by resin transfer molding (RTM) Journal
of Composite Materials, Vol. 38, No. 3, pp 195-226, 2004.

52

21.

22.

23.

24.

25.
26.

27.
28.
29.
30.

Ricco, L., Russo, S., Orefice, G., Riva, F., (1999) Anionic poly(-caprolactam):
relationships among conditions of synthesis, chain regularity, reticular order, and
polymorphism, Macromolecules, Vol 32, pp. 77267731.
Russo, S., Imperato, A., (1995) The fast activation of -caprolactam polymerization in
quasi-adiabatic conditions, Macromolecular chemistry and physics, Vol 196, pp. 3297
3303.
van Rijswijk, K., van Geenen, A.A., Bersee, H.E.N., Textile Fiber-Reinforced Anionic
Polyamide-6 Composites Part II: Investigation on Interfacial Bond Formation by Short
Beam Shear Test, Composites: Part A (2009)
Parlevliet P.P., Bersee H.E.N., Beukers A. Residual stresses in thermoplastic
composites A study of the literature Part I: Formation of residual stresses.,
Composites Part A, Vol. 37, pp. 1847-1857, 2006.
Kohan M.I. (Editor), Nylon plastics handbook, Hanser, New York (1995).
Ramazani, A.S.A., Mousavi S.A.S., Investigation of vacuum annealing effects on
physicalmechanical properties of thermoplastic parts, Materials and design, Vol 26, pp.
8993, 2004
Jarecki, L., A. Ziabicki, Polymer, Vol 18, pp. 1015, 1977.
Young, R.J., Lovell, P.A., (1991) Introduction to Polymers, CRC Press, 2nd Edition.
Gogolewski, S., Gasiorek, M., Czerniawska, K., Pennings, A. J., Annealing of meltcrystallized nylon 6, Colloid & polymer science, Vol 260, pp. 859-863, 1982.
Composite Materials for Wind Power Turbine Blades (Annual Revision Material Research
2005. issue 35, p. 505-538

53