Modelling of cure kinetics

INTRODUCTION:

• Rotor blades are fabricated by vacuum assisted resin infusion molding

(VARIM) process using amine cured epoxy resins.

• The rate of resin cure depends on the process temperature and the
exothermal heat generated during curing process.

• Simulation of kinetics of amine cured epoxy resin formation based on trial

and error has always been an expensive affair.

• Modern researchers use computer simulation models for designing the

process for optimizing the process parameters is the development of a
suitable kinetic model.
INTRODUCTION:
• In general, cure kinetic models can be classified in two categories,
1. Mechanistic kinetic model
2. Empirical/ phenomenological kinetic model.

• An accurate mechanistic model to describe the curing kinetics is impossible

because of the fact of the large variations in the resin formulations and most
often, the exact formulation is not known.

• Efforts have been directed towards establishing phenomenological models

for epoxy resins using differential scanning calorimetry (DSC).
 MODELS AVILABLE FOR KINETIC STUDY:

•nth order model for curing reaction of thermoset

 E 
 
k  T   Ae  RT 

where k(T) is kinetic rate constant following Arrhenius temperature dependency

• Kamal and Sourour et al.(1973) came up with an autocatalytic model, shown as:

d
dt

 k1  k 2 m 1    
n

• As extension to Kamal’s model accounting for increased accuracy at later stages of

cure by Karnakas et al. (2000) shown below:

d
 k 0 1    1  k1 m 1    2
n n

dt
Experiment

Study of cure kinetics of composites

a. Sample Preparation for DSC analysis
• DSC analysis:
• Dynamic scan
• Isothermal scan
b. Modeling for evaluation of cure kinetics from isothermal scan of DSC
Cure kinetics study

Materials for DSC analysis:

• Epoxy resin (YDL-680)
• Hardener (TH722510)

Procedure:
• Epoxy Resin and hardener is mixed in 100 : 33 (by Wt%)
• Mixing time kept constant for 5 min.

Curing study was performed using Differential Scanning Calorimetry (DSC):

– Dynamic analysis
– Isothermal analysis
• Dynamic DSC scan with varying temperatures was also performed and heat flow at various
temperatures was obtained

• Reaction onset is 50°C,

Peak heat flow temperature is 100°C, isothermal temperatures chosen within this range

• 70°C, 75°C, 80°C and 85°C

are considered as isothermal
temperatures

• Justification for not selecting the temperature below or around 50°C is that the reaction is too
slow and will take an appreciable time for completion.
• whereas above 100°C the rate of reaction is very high, and a significant part of the curing is
assumed to be complete before the attainment of the isothermal temperature.
• Curing was carried out under isothermal conditions and heat flow vs. time was recorded
 Results and discussion

• Higher the curing temperature, higher is the peak heat flow value attained.

• It shows that the time taken to reach the peak heat flow decreases with increasing curing
temperature
 Calculation approach
• Heat flow vs. time data is obtained from DSC for various temperatures

• Area under the isothermal heat flow curve gives total heat of curing reaction, ∆H T, expressed
as
H T   Q t  dt

• Instantaneous degree of cure α(t), can be obtained by

H (t )
 (t ) 
H T
• Where ∆H(t) is amount of heat released up to time ‘t’, expressed as:
t
H  t    Q t  dt
0

• Furthermore, the rate of cure dα/dt, are the slopes to the degree of cure vs. time curve
• The total heat of reaction ΔHT was estimated from the exotherm area under the respective
normalized heat flow curves.

Isothermal ΔHT, Total Heat of

Temperature, °C Reaction, W-min/g
70 6.31
75 6.33
80 6.56
85 6.86

• ΔHT at various isothermal temperatures, and these values of total heat of reaction are almost
identical.

• It is found that the values of the total heat of the reaction are almost identical for all
temperatures indicating that the total heat of the reaction is independent of
the temperature.
 Degree of cure plots

 Sharp and steep rise at initial stages of cure

 At any instantaneous time, higher is the isothermal temperature, higher is the degree of
cure

 Rate of cure decreases with degree of cure, maximum and then tends to zero

 For the given conversion, higher is the isothermal temperature, higher is the cure rate.
Modelling of cure kinetics at different isothermal temperatures

 Parameters for the model equations are determined by non-linear regression analysis

 Both models fit the data well except at the initial stages for 70 and 75 °C
            
Isothermal Empirical rate Empirical rate Empirical Empirical Coefficient of
temperature constant k1 constant, exponent, exponent, determination
(oC) (min-1) k2 (min-1) m n R2
 
70 0.098 -0.148 4.00 0.92 0.99
75 0.111 -0.142 3.56 0.95 0.99
80 0.166 0.644 1.66 2.17 0.98
85 0.261 0.540 1.70 1.74 0.98
Kamal and Sourour model parameter values by non linear regression analysis

           
Empirical
Isothermal Empirical rate Empirical rate Empirical Empirical R2
exponent,
temperature constant constant exponent, exponent,
m
(oC) k0 (min-1) k1 (min-1) n1 n2
 
70 0.099 1.779 2.48 3.28 2.36 0.98
75 0.110 0.626 2.36 2.59 1.67 0.99
80 0.166 0.645 2.09 2.20 1.71 0.99
85 0.251 0.713 4.39 1.70 0.94 0.99
Karnakas model parameter values by non linear regression analysis
Conclusions
• Cure kinetics of epoxy resin is modelled, and it is observed that Kanakas
(2000), Kamal and Sourour (1973) models fit well with the experimental
data.

• Rate of cure equation w.r.t to parameter value for isothermal temperature

can be used for the computer simulation models and designing the
process for optimizing the process parameters.
 References
• M. R. Kamal, S. Sourour, Polym. Eng. Sci. 1973, 13, 59.

• P. I. Karkanas, I. K. Partridge, J. Appl. Polym. Sci. 2000, 77,1419.

• A. Sahli, R. Granger, J. M. Vergnaud, Thermochim. Acta 1996,285, 277.

• S. Husseinsyah and M. Mostapha, Malaysian Polymer Journal,2011 , 6, 87.

• F. R. Tollens, L. James Lee, Polymer 1993, 34, 29.

• L. Zhao, X. Hu, Polymer 2007, 48, 6125.

• A. Arrillaga, A. M. Zaldua, R. M. Atxurra, A. S. Farid, Eur.Polym. J. 2007, 43, 4783.

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