Effect of quenching on the crystallinity of PVDF

Objective:
Understanding the effect of quenching on the crystallinity of PVDF
Introduction:
One of the most important properties of semi-crystalline thermoplastics (like
polyethylene terephthalate (PET), poly vinylidene fluoride (PVDF), nylon, polyethylene,
polypropylene, PES, PEEK) is the polymers percent crystallinity. This refers to the overall
level of crystalline component in relationship to its amorphous component. The percent
crystallinity is directly related to many of the key properties exhibited by a semi-crystalline
polymer including brittleness, toughness, stiffness or modulus, optical clarity, creep or cold
flow, barrier resistance (ability to prevent gas transfer in or out) etc.
PVDF is a speciality polymer showing piezoelectric properties. Due to its strength,
resistance to solvents, acids, bases, etc. it is used in piping, sheet products, insulator for wire
and so on. The piezoelectric properties of PVDF make it useful in actuator and sensor
application. It finds application in chemical, defence and semiconductor industries.
PVDF exists in four crystalline forms, , , and . The assessment of a polymers
percent crystallinity can be most easily performed using differential scanning calorimetry
(DSC) which measures the heat flow into or from a sample as it is either heated, cooled or
under isothermally (see Figure 1).
Procedure:
To perform percent crystallinity measurement, approximately 5 mg of the sample
PVDF samples were used. The following test conditions are used to measure the samples
crystallinity:
Sample 1:As obtained pellets
Step 1. First heating: room temperature (RT) to 280 C under N2 atmosphere at 10 K/min
Step 2. Hold for 2 min @ 280 C
Step 3: Cool to RT at 10 K/min under N2 atmosphere
Step 4: Second heating: RT to 280 C under N2 atmosphere at 10 K/min (Optional)

Sample 2: Quenched disc

Repeat the above test by quenching samples at maximum possible rate (i.e. 100K/min)

The heats of melting, Hm, and crystallization, Hc, are determined by integrating the areas
(J/g) under the peaks. Depending upon the samples given thermal history, a cold
crystallization exothermic peak may or may not be observed during the DSC experiment. The
percent crystallinity (% Xc) is then determined using the following equation:

% Xc = ([Hm or Hc] / Hm

In this equation, the heats of melting and crystallization are in terms of J/g. The term Hm is
a reference value and represents the heat of melting if the polymer were 100% crystalline.
(104.5 J/g)
Report:
Report the % Xc of PVDF under two processing conditions.

Figure 1: Typical DSC scan of PET bottle