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Nonisothermal melt crystallization of PHB/babassu compounds

Kinetics of crystallization

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Abstract

Poly(3-hydroxybutyrate) (PHB)/babassu compounds were prepared in a laboratory internal mixer with 10, 30, and 50 % by mass of fiber content. Nonisothermal melt crystallization behavior of PHB/babassu compounds was investigated using differential scanning calorimetry, and crystallization parameters were determined at cooling rates ranging between 2 and 32 °C min−1. Adding babassu fiber affected the melt crystallization behavior of PHB, and increasing filler content from 10 to 30 % has significant effects on the thermal characteristics of the system. Further increase in filler content from 30 to 50 % filler content has no effect on crystallization temperature and rate, but it has important positive consequences, once there is a considerably latitude in choosing the actual filler level in highly loaded PHB/babassu compounds without affecting processing characteristics. The melt crystallization kinetics of PHB/babassu compounds was analyzed by three empirical models widely used to represent nonisothermal polymer crystallization data: Pseudo-Avrami, Ozawa, and Mo. Kinetics analyses indicate that the Pseudo-Avrami model represented well the experimental data for both compounds in a wide interval of temperature, conversion, and cooling rates; the Ozawa model with two different sets of parameters, for low and high cooling rates, was found to correlate the data equally well, but over limited ranges of the variables, and the model proposed by Mo and collaborators did not adequately represent the experimental data for the systems and conditions tested.

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Abbreviations

c :

Crystallization rate

c 0.1–99.9% :

Crystallization rate measured between 0.1 and 99.9 % of mass transformation

c 20–80% :

Crystallization rate measured between 20 and 80 % of mass transformation

c max :

Maximum crystallization rate (at T c)

E 0 :

Total latent heat released or absorbed by the sample during the crystallization or melting event

F :

Mo rate parameter

J :

DSC output heat flow rate of thermal energy exchanged between sample and the surroundings

J 0 :

Virtual baseline during a phase change event

K′:

Pseudo-Avrami rate parameter

m :

Ozawa exponente

MFR:

Melt flow rate

M n :

Number average molar weight

n′:

Pseudo-Avrami exponente

t 1 :

Onset time of the crystallization event

t 2 :

Endtime of the crystallization event

T :

Temperature

T 0.1% :

Temperature to attain 0.1 % of crystallized fraction

T 50% :

Temperature to attain 50 % of crystallized fraction

T 99.9% :

Temperature to attain 99.9 % of crystallized fraction

T c :

Peak crystallization temperature

T 0 :

Initial temperature on the start of the crystallization process

X :

Relative crystallinity or crystallized fraction during a crystallization event

X c :

Degree of crystallinity

x(t):

Crystallized fraction as a function of time

x(T):

Crystallized fraction as a function of temperature

∆H c :

Specific latent heat of crystallization

\(\Delta H_{\text{m}}^{0}\) :

Equilibrium melting enthalpy of 100 % crystalline resin

α :

Mo exponente

ϕ :

Heating/cooling rate

κ :

Ozawa rate parameter

ρ :

Density

τ :

Crystallization time

τ ½ :

Crystallization halftime (time to attain 50 % fractional crystallization), inversely proportional to mean crystallization rate between 0 and 50 % fractional crystallization

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Acknowledgements

The authors are indebted to CNPq (Brasília/DF, Brazil) and FACEPE (Recife/Pernambuco, Brazil) for the financial support and to PHB Industrial (Serrana/São Paulo, Brazil) and MAPA Representations (São Luis/Maranhão, Brazil), respectively, for the donation of polymer and filler.

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Authors and Affiliations

  1. Department of Materials Engineering, Federal University of Campina Grande, Campina Grande, PB, CEP 58429-140, Brazil

    Maria B. C. Vitorino, Pâmela B. Cipriano, Eduardo L. Canedo & Laura H. Carvalho

  2. Department of Materials Engineering, Federal University of Paraíba, João Pessoa, PB, CEP 58051-900, Brazil

    Renate M. R. Wellen

  3. Pernambuco Institute of Technology, Recife, PE, CEP 50740-540, Brazil

    Eduardo L. Canedo

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  1. Maria B. C. Vitorino
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  2. Pâmela B. Cipriano
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  5. Laura H. Carvalho
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Correspondence to Renate M. R. Wellen.

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Vitorino, M.B.C., Cipriano, P.B., Wellen, R.M.R. et al. Nonisothermal melt crystallization of PHB/babassu compounds. J Therm Anal Calorim 126, 755–769 (2016). https://doi.org/10.1007/s10973-016-5514-7

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