Shrinkage Modeling of Polyester Shrink Film

WAYNE K. SHIH

Packaging Research Laboratory

Eastman Chemical Company Kingsport, Tennessee 37662
A model was developed to q u a n w the thermal shrinkage behavior of polyester shrink film under isothermal and nonisothermal conditions. This model employs the straightforward first order reaction kinetics to an otherwise microscopically complex relaxation process. It offers three unique parameters for quality control and material specification of shrink fl. the isothermal condition, the inducim In tion time, the shrink constant, and the ultimate shrinkage are the three parame ters used by the model to quantify the shnnkage of shrink film under an elevated but constant temperature. In the nonisothermal condition, the shrink film is heated using a constant heating rate. Three parameters, which are the onset shrbk temperature, the shrink constant, and the ultimate shrinkage, characterize the shrinkage of shrink film. The model fits the experimental data very well. The thermal shnnkage of several polyester homopolymers, copolymers, and polyester blends was investigated and compared to that of poly(viny1 chloride) ( W C ) shrink fl. im Two polyester blends containing glycol modifled polfiethylene terephthalate) (PETG)copolyester behave similar to W C in shrinkage behavior. The effect of stretch temperature, stretch ratio, and stretch rate on the shrinkage characteristics of oriented PETG film was also studied. The stretch temperature has the highest influence on the shrinkage behavior of oriented film.

INTRODUCTION

hrink film is widely used as tamper-evident (resistant) seals for food and pharmaceutical products and as primary labels on various bottles, including soft drink. Although polyvinyl chloride ( W C ) currently dominates the market, shrink film can also be made of oriented polystyrene (OF'S), oriented polyethylene (OPE), oriented polypropylene (OPP), and oriented polyesters. As a result of the environmental pressure on W C , the recyclability of polyester is an attractive alternative. However, the thermal shrinkage of oriented polyester fl is not im well known. Thus the goal of this work was to develop a model that can be used to quantify the shrink film with meaningful parameters. The thermal shrinkage of various polymeric materials has been investigated: PET (1-6). PE (7, 8).PEN (9), PI (10, 1 l), PS (12). and W C (13, 14). The shrinkage is usually measured by placing the specimens in an oil/water bath or a hot air oven at a constant temperature. On the other hand, thermal mechanical analysis (TMA) is the most popular technique to obtain the thermal shrinkage under a constant heating rate. TMA is often used to study the shrinkage mechanisms and shrinkage modeling as well. Kambe et a (10,11) used a two-state model to L study the kinetics of the thermal shrinkage of polyimide and polystyrene. The activation energy from the

extended state (higher energy) to the contracted state (lower energy) was calculated from TMA results at various heating rates. Pakula and his coworkers (2.3) used a four-state model to describe the temperature (constant heating rate) and time (constant temperature) dependencies of shrinkage forces in oriented amorphous polymers. They then applied a multi-state mechanical model to simulate the shrinkage stress of amorphous polymers in terms of the internal stress relaxation (6). A detailed review on the thermal shrinkage of oriented polymers was written by m n a d e l and Kryszewski (15). However, none of the models are capable of quantifying the thermal shrinkage of oriented polymers. This leads to the following theoretical development for modeling thethermal shrinkage of uniaxially oriented film under isothermal and nonisothermalconditions using the concept of first order reaction kinetics.

THE MODEL
The shnnkage of amorphous polymers can be envisioned using a simple model, which is a combination of the Kelvin unit (the spring, S,,and the dashpot, D , , in parallel) and the Maxwell unit (the spring, q, and the dashpot, D,, in series) as shown in FYg. 1 . The mathematical response of this combined model will not describe the shrinkage of the polymers. However its concept is used to explain the states during
1121

POLYMER EbtG#MERIUG AND SCIENCE, JULY 1994, V d . 3 , NO. 14 4

Wayne K. Shih

a
2

l d

/
Fg. 1 . A combined model to describe the shrinkage of uniaxially oriented amorphous polymeric fdms.

the relaxation process. The Kelvin unit is used to dictate the internal stress of oriented polymers. The Maxwell unit monitors the shrink stress. Initially, the Kelvin unit is stretched at a higher temperature above the glass transition temperature, Tg, then frozen at the room temperature. The viscosity of the dashpot, D,, is low at the temperature above Tg so that the Kelvin unit is stretched easily. The extended spring S, is then frozen owing to the high viscosity of the extended dashpot at the room temperature. The internal stress, indicated by the stress of S,, is therefore the highest at this state. A relaxed Maxwell unit is then attached to the extended Kelvin unit to monitor the shrink stress. The combined model is then fixed at both ends. As the temperature rises as a result of heating, the viscosity of the dashpot D , decreases. The spring S, starts to retract owing to its high internal stress. The spring S, is then extended, which indicates the increase of the shrink stress. The internal stress of S, decreases and the shrink stress of S , increases continuously until the viscosity of dashpot D, is so low that D, starts to extend and the spring S, will not extend any further but start to relax. This implies that the shrink stress increases first, reaches a peak, and declines, Finally, both springs are in their relaxation states. If the maxwell unit is not attached to the extended Kelvin unit, the Kelvin unit is not fixed and relaxes freely without constraints. The shrinkage therefore occurs during the relaxation of the Kelvin unit. The shrinkage will not start until the temperature reaches a critical onset temperature To,where the spring stress of S, overcomes the viscous retardation of the dashpot D,. The internal stress of S, is higher when the polymer is stretched at a lower temperature because there is less chance of relaxation before being frozen at the room temperature. The film stretched at low temperatures tends to shrink faster and to a greater extent as it is heated up. FLgure 2 shows the schematics of internal stress, shrink stress, and shrinkage as a function of temperature. The internal stress is the highest at low temperature and decreases rapidly with the increasing temperature. The shrink stress increases initially, reaches a peak, and decreases afterward as described before. The shrinkage curve is normally sigmoidal for
1122

Temperature, "C
Fg. 2. Schematics o the internal stress, shrink stress, and f
f shrinkage o uniaxially oriented amorphous polymeric Jlms a functions of temperature. s

most of the amorphous polymers. It reaches the ultimate shrinkage and declines accordingly as a result of overheating. Strain-hardening polymers during stretching may develop a second shrink force peak owing to strain-induced crystallization. Our model will be limited to amorphous polymers without strain-hardening effects. The shrinkage s of polymer films is defined as
s=-

1,10

where 1, is the original length of the specimen before heating, and 1 is the length of the specimen during heating. The ultimate shrinkage, g , the maximal shrinkis age of the film before it starts to expand as a result of overheating. The ultimate shrinkage can be expressed by the following equation:
s, = 1 0

1,-

where I, is the final length of the film before overheating.

Kinetics of Isothermal Shrinkage

Assume that the shrinkage follows the first order reaction. Namely, the change (first derivative) of concentration with respect to time, d C / d t , is proportional to the concentration, C.
d C / d t = - kC

(3)

where C = 1 - l J l o - I, is equivalent to the fraction of the unreacted reactant. Rearrange Eq 3 and integrate the equation using the following boundary
POLYMER ENGINEERING AND SCIENCE, JULY 1994, Vol. 34, No. 14

Shrinkage Modeling o Polyester Shrink Film f conditions ( BCs): BC1 t = to. BC2 t = t , We have
(4)

C= l ( l = l o ) c=c

where K = k/4 (note that K will be replaced by k later for simplicity). S m l r to the derivations in the isothermal case, iia the shrinkage kinetic equation can be expressed as follows: s=&(l-exp[-~(T-T~)])
S90 =

T>To

(14)

%( 1 - eXp[ - K (90 - T o ) ] )

(15)

or lnC= - k ( t - to) or
C = exp[ - k( t - to)]
(5)

where
s is the shrinkage. s, is the ultimate shnnkage before overheating (Fig. 2). sgo is the shrinkage at 90C. K is the shrink constant under a constant heating rate. T is the shrink temperature. T is the onset shrink temperature (Fig. 2). o

(6)

Substitute the definition for C into Eq 6, then

-=

1,-

' L
L

exp[ - k( t - to)]

(7)

Equation 7 can be rearranged into the following form: lo-L

1 0

1,-1
1 0

1,1 0

= exp[ - k( t -

to)]

If we substitute the definitions for the shnnkage and the ultimate shrinkage from Eq 1 and Eq 2 into Eq 7, we have
%-- S

- 1-s/s,=exp[-k(t-t0)l
s=s,(l-exp[-k(t-t,)])

s,
or

(9)

t > t o (10)

where

s is the shrinkage at time t. s, is the ultimate shrinkage at time &. k is the shrink constant. t is the shrink time at a constant shrink temperature. to is the induction time at a constant shrink temperature.
Although the polymer chain relaxation occurs even at room temperature, noticeable shrinkage in a limited time is achievable only at elevated temperatures. There are three important features to characterize an isothermal shrink curve. They are the induction time, to; the slope of the curve controlled by the shrink constant, k; and the ultimate shrinkage, SL.

The important features of a shrink curve under a constant heating rate are the onset shrink temperature, To; the slope of the curve controlled by the shrink constant k; and the ultimate shrinkage, 6. This equation is valid when the shrink temperature is greater than the onset temperature. The shrinkage at temperatures below the onset temperature is regarded as zero. This model demonstrates the shrink features using the onset temperature, the shrink constant, and the ultimate shrinkage. The onset temperature dictates the temperature at which the film starts to shrink. This number is critical when a low temperature shrinkage is desirable, such as for heat-sensitive foods and packages. The shrink constant is also an important feature that tells how fast the film will shrink. Normally, the shrink rate is slow enough such that the letters or symbols printed on the film will not be distorted. Figure 3 illustrates the shrink curves (shnnkage vs. shrink temperature) using the model under the non-

To= 60C

Kinetics of Nonisothermal SMnlrage

If the film shrinks under a constant heating rate,

4, the kinetics are still assumed to be the first order of reaction. The heating rate, 4, can be written as 4 = dT/dt (11)
or dt = dT/+ Substituting Eq 12 into Eq 13, we have dC/dT= - kC/4 = - K C (13)
CUNeS.

(12)
Temperature, "C
Fig. 3. The effmt o the shrink constant on the model shrink f

POLYMER ENGINEERING AND SCIENCE, JULY 1994, Vol. 3 , No. 14 4

1123

Wayne K. Shih

isothermal condition. The onset temperature and the ultimate shrinkage are held constant but the shrink constant changes. Shrink curves with a larger k value rise sharply to a higher shrinkage. On the other hand, curves with a smaller k rise slowly and reach a lower shrinkage at comparable temperatures. The higher the shrink constant, k , the higher the shrink rate. A shrink film with a high shrink rate is normally difficult to control and will distort labels. Figure 4 shows the effect of the onset shrink temperature with fixed ultimate shrinkage and shrink constant. Lower shrink temperatures can be used to obtain the same amount of shrinkage earlier if the lower onset shrink temperature film is used. This is a must for (1) heat-sensitive shrink packaging, where the packages cannot be heated at higher temperatures, and (2)short shrink tunnels, where higher shrink temperatures cannot be achieved because of short residence time. Figure 5 demonstrates the effect of the ultimate shrinkage on the shrink curves while the onset temperature and the shrinkage constant remain constant. A higher ultimate shrinkage may be required in certain applications, such as tamper-evident seals in the neck area of the bottle. Three shrink parameters can be the intrinsic properties of polymers so that shrink films made of different polymers behave differently. However, these three parameters can be modified to a certain extent by changing the production conditions. Therefore, balance or optimal features of shrink films can be tailored according to the application requirements. The following experiments are designed to demonstrate the intrinsic nature of these three parameters as well as the effect of several production conditions on these parameters.
EXPERIMENTAL

80

T0=60"C k = 1

s_= 80%

i
60%

0 50

L
60

70

80

90

100

Temperature, "C
Frg. 5. The effect o the ultimate shrinkage on the model f
shrink curves.

The polymeric materials used in this work, except for PVC, were manufactured by Eastman Chemical

s_= 60% k = .1

6e

Company, Kingsport, Tennessee. They are (1) homopolymers: Kodapak@ PET 7352 and PET 9663, (2) copolymers: Kodar@PETG 6763, and Kodabond@ 5116 and 13162, and (3) blends: (a) 2-component blend: 10 wt% Kodabond 51 16 + 90 wt% PETG 6763 and (b) 3-component blend: 5 wt% Kodabond 51 16 + 15 wt% PET 9663 + 80 wt% PETG 6763. Unless specified, all polymers and blends were extruded into film and then stretched at 90C into shrink film using a T. M. Long film stretcher (T. M. Long Inc., Sommerville, New Jersey). The stretch ratio is either 3 x 1 or 4 X 1, as indicated in each figure. The nominal thickness of the stretched film is 2 mils. The stretched film was then cut into 100 x 100 mm specimens. The specimen was placed in a free shrink holder, free from contact with the edges of the holder, and immersed in a constanttemperature water bath at (1) 65, 70, and 75"C, respectively, from 1 to 180 s at each temperature in isothermal experiments, and for (2) 30 s at 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90C. respectively, for nonisothermal experiments. The specimen was then removed from the water bath and quickly dried with wipes at room temperature. The thermal shrinkage in the stretch direction was then recorded by measuring the linear dimension, 1, of the specimen in mm using a ruler. The temperature of the bath was recorded as well. A minimum of two specimens is necessary at each test temperature (ASTM D2732-83). The percent free shrinkage is then calculated as follows:
s,%=100- 1

100

x l o o = 100- 1

(16)

50

60

70

80

90

100

110

Temperature, "C
Q. 4. The effect o the onset shrink temperature on the f model shrink curves.
1124

The experimental data were curve-fitted to Eq 14 using the Marquardt nonlinear least square method (16). Three parameters-the ultimate shrinkage, %; the shrink constant, k (replaced K in Eq 14); and the
POLYMER ENGINEERING AND SCIENCE, JULY 1994, Vol. 34, No. 14

Shrinkage Modeling o Polyester Shrink Film f

onset shrink temperature, To-of the model are therefore obtained from the curve fitting. Note that the specimen was not heated continuously under a constant heating rate. However, the nonisothermal model is still applicable in this case. The glass transition temperature w s obtained by DSC. a
RESULTS ABlD DESCUSSION

e-The shrink curves of PETG. stretched into 3 x 1 at 85C. tested at 65. 70,and 75C.respectively, are shown in Fig. 6. The isothermal shrinkage model (solid Unes) fits the data very well. The corresponding shrink parameters-the induction time, to;the shrink constant, k and the ultimate shrinkage-are tabulated in T b e 1. The PETG film shrinks relatively al slowly (a small k) at 65Cand its ultimate shrinkage is also low (a small 8) this temperature. However, at it has the longest induction time. In general, the higher the test temperature, the shorter the induction time accompanied with higher shrink rate and ultimate shrinkage. A similar induction time of the shrink stress at constant temperature for PET was 7. observed by Trznadel (1 )
Nodsothermal Shrinkage

of W C shrink f l . T b e 2 shows the shrinkage i m al parameters for various polymers and blends. Two polymers must have close matches in corresponding shrinkage parameters to have similar shrinkage. For some oriented polymers, such as polyester homopolymers, the shrinkage never reaches the curve-fitted ultimate shnnkage because of the self-leveling effect, thus the calculated shrinkage at W " C ,sw, is a better parameter for comparison purposes.
WC

The shrink curve of W C stretched to 3 x 1 at 90C is illustrated in Flg. 7. The shrink parameters of W C shrink fl are displayed in T b e 2, where To is the im al intercept of fitted curves on the temperature axis.The model (solid line) fits the data very well except at the initial tailing (dotted line) of the shrink curve. The
Table 2. NonisothermalShrink Parametersfor Various Polymers and Blends. Material
PVC, 3 x 1@Wac Kodabond 5116, 4 X 1@70C Kodabond 13162, 4 X 1@70C PET7352,4xl@WC PET9663,4X1@90C PETG6763, 3 X l @ W C PETG 6763,3 x 1@100"C PTG 6763, 3 X l@llOC PETG6763,3xl@lWC PETG 6763, 4 X 1@90C 90% PETG 6763 + 10% Kodabond 5116, 3 X 1@90C 80%PETG5116+ 15% PET 9663 + 5% Kodabond 5116, 3 X 1@90"C

T,,"C
63.5 44.8 45.3 72.1 68.2 65.0 64.7 64.3 63.7 68.6 63.7

k,"C-' sgo,%
0.10 0.12
0.06 0.008

%,,%

58.4 69.7 70.9 12.1 11.4 67.5 57.2 49.9 47.0 72.4 57.9

62.0 69.9 76.4 100 100 68.3 62.9 61.2 72.3 82.0 60.8

Since the polyester shrink film is aimed to be an alternative to W C shrink film, the shnnkage data of polyester shrink film will be compared with those

0.006
0.18 0.10 0.07 0.04 0.10 0.12

8o

75C

64.7

0.11

5. 29

56.9

0 PVC. 3x1 090C A Kodabond 5116,4x1 0 70C

0 PET 9663.

4x1 0 90C

0
0 30

60

90

120

150

180

210

Time, sec FYg. 6. Isothermal shrwc curves o PEn; stretched into 3 X f

1@85C.

Table 1. Isothermal Shrink Parametersof PETG Film Oriented I t 3 x 1 at 85C. no lest Tmp.mture, "C
65 70 75 t, ,s
24.7 10.2 1.8 k , s-

'

t, %
38 52 62

40

50

60

70

80

90

100

0.009
0.049 0.126

Temperature, "C
FYg. 7. l X e shrink c~uvesf miaxially oriented K o d a b o n d s , o we, andPETflm.
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POLYMER EMW#EER#NGAND SCIENCE, JULY 1994, vd. 3 ,No. 14 4

W a y n e K. Shih

dotted line is formed by spline fitting all adjacent data points. This model is more applicable to polyester shrink film. A refined model better describing the tailing of shrink curves as well as the shrinkage of shrink films made of other polymers will be available elsewhere ( 18).
Kodabond Copolyester

The Tg of Kodabond 5116 is 54C and 58C for Kodabond 13162. Both Kodabond shrink films have about the same onset shrinkage temperature, To, and shrinkage at 90C, sg0 (Fig. 7). Kodabond 51 16 film has a higher shrinkage constant than Kodabond 13162film. The higher the shrinkage constant, k, the steeper the shrinkage curve. Since Kodabond is compatible with PETG 6763 from DSC analysis, it is utilized to lower the Tg of PETG 6763 (80C) when blended. The onset shrinkage temperature of the shrink film made of the polymer blend is therefore reduced.
Polyester Homopolymer Figure 7 shows that the onset shrinkage temperature of PET 7352 film is about 72C. It shrinks about 12% at 90C (Table 2). The shrinkage of PET 9663, when stretched into 4 X 1 at 90C, is almost identical to that of PET 7352 (Table 2). The model usually does not work well for these crystalline polymers having self-leveling characteristics during stretching. These low shrinkage polymers are used to reduce the higher shrinkage polymers, such as PETG 6763, when both polymers are blended together. PETG Copolyester F g u r e 8 illustrates the thermal shrinkage curves of oriented PETG 6763 film. PETG shrink film has higher onset temperature, To. shrink constant, k , and ultimate shrinkage, %, than the corresponding values of

PVC (Table 2). This indicates that the oriented PETG film will shrink at higher temperature, faster, and to a greater extent compared to PVC shrink film. Ideally, the three shrinkage parameters-onset shrink temperature, shrink constant, and ultimate shrinkage-of the polyester shrink film should be identified to those of PVC shrink film. The main concerns in using PETG shrink film are: (1) the onset shrink temperature of polyester shrink film is higher than that of W C shrink film and (2) PETG shrinks too fast. Low temperature shrinkage is desirable for the integrity of heat sensitive packages (including the packaging material and content). Slow shrinkage allows better control in quality. For shrink sleeve application, the minimum ultimate shrinkage is about 50% in TD (transverse direction, hoop direction) and about 5% in MD (machine direction, axial direction). A 5% shrinkage in the MD direction is desirable to compensate for the thermal relaxation of shrink film in this direction during heating. The shrink sleeve is placed around the container before entering the shrink tunnel. Only some portions of the film will be in contact with the wall of the filled container during heating. The temperature of the film will be lower if in contact with the container due to better heat conduction. The portions not in contact with the container will have a higher temperature. A fast shrink rate is especially undesirable because the film tends to form more and larger bubbles or wrinkles around the container. This uneven heating will not cause problems if the shrink film shrinks relatively slowly, as does W C ( 14). The problem, which may be present in the fastshrinking PETG film, causes the distortion of label symbols or characters.

Polyester Blends

3x1 Q90"C 0
V PETG 6763
90% PETG 6763

10% Kodabond 5116

BO%PETG 6763+15%PET 9663+5%Kodabond 5 1 16 0 PVC

0
60
70

80

90

100

Temperature, " C
Q. 8. The shrink curves o uniaxially oriented PETG, W C , f and polyester blendjilms.
1126

In order to utilize the existing shrink tunnel for PVC without changing conditions drastically, the onset temperature and steepness (shrink constant and ultimate shrinkage) of the PETG shrink curve need to be modified so that its thermal shrinkage behavior will be close to the behavior of PVC shrink film. A novel approach is to blend PETG with a low Tg and/or a low shrinkage polyester. The low Tg material can be Kodabond 5116 (54C) or 13162 (58C). PET homopolymer is the candidate for low shrinkage material, as shown in Fg. 7. The miscible blends have one single Tg from DSC measurement. In Fig. 8, the shrink curve of the two-component blend composed of 90% PETG and 10% Kodabond is very close to the PVC curve. Low shrinkage PET can be blended with PETG so that the steepness of the curve can be lessened. The shrink behavior of this three-component blend, 80% PETG 6763 + 15% PET 9663 + 5% Kodabond 51 16, is lower than but almost follows that of PVC ( R g . 8). Table 2 also demonstrates that both two- and three-component blends have very similar corresponding shrink parameters compared to W C . It is feasible that the PVC curve can be closely matched using PETG blends by adjusting the blend composition.
POLYMER ENGINEERING AND SCIENCE, JULY 1994, Vol. 34, No. 14

Shrinkage Modeling of Polyester Shrink Film Stretch Rate Effect

The Shrinkage characteristics of PETG shrink film do not change with stretch rate, as shown in Fig. 9. The stretch rates were changed from 5 in./s to 20 in./s with an increment of 5 in./s. It may not be concluded that the stretch rate has no effect on the shrinkage of film. However, the effect of stretch rate is not observed in this practical range for shrink film production.
Temperature Effect

The shrink curves of PETG fl stretched into 3 x 1 im at various temperatures ranging from 90C to 120C are illustrated i Rg. 10. The onset shrink temperan ture does not change for all practical purposes with stretch temperature. However, the shrink constant and ultimate shrinkage decrease significantly with increasing stretch temperature. It is expected that polymer chains, when stretched at higher temperature, will relax more after stretching owing to higher mobility at higher temperature. Thus the polymer stretched at higher temperatures will shrink less than the polymer stretched at lower temperatures. As shown in Ftg. 10 and Table 2, to match both the shrinkage constant and the ultimate shrinkage of W C . PETG has to be stretched at 100C.The shrink curve but not the onset shrink temperature of W C can be matched closely by adjusting the stretch temperature. The adjustment of stretch temperature cannot lower the onset shrink temperature. The onset shrink temperature can be lowered by blending in a low Tg polymer, such as Kodabond, as described earlier.
Stretch Ratio Eflect

Alm is normally poor at lower stretch ratios owing to the lack of self-leveling characteristics. In other words, the thickness variation across the stretch direction is high if the stretch ratio is too low. A stretch ratio of above 4 x 1 was found to be an optiim mal condition. F l stretched at a higher stretch ratio (4 x 1 has a higher onset temperature and ) a higher ultimate shrinkage as compared to Alm stretched at a lower ratio (3x 11, as seen in Q. 1 1 and T b e 2. This higher onset temperature is not al desirable. However, a compromise has to be made between stretchability and onset shnnkage temperature. A film of uniform thickness is much preferred, of course, as an important quality control. S m l r iia phenomena were also seen in blends. It becomes more difficult to match W C film using blends ori-

0 PETG 90C
0 PETG 100C
V PETG 120C

60

70

80

90

100

In order to achieve a minimum ultimate shnnkage of about 50%. the stretch ratio is usually greater than 2 x 1. However, the uniformity of stretched PETG

TEMPERATURE, "C

Fig. 10. The effectof stretch temperature on the shrinkage of

uniavially oriented P E n ; J u r n
100
1 I I

0 PETG 5 " / s 0 PETG lO"/s

0 PETC 3x1B9OoC
0 PETC 4xlO90'C
80
0 PVC 3x1890-C

9J M

60

rd

c m
2o

'c

40

t
70

20

60

80

90

100

60

70

80

90

100

TEMPERATURE, "C

Temperature, "C

Fig. 9. The effmto stretch rate on the shrinkage o miaxially f f oriented Pmfilrn
#OLYMER E N G f " 0

a.1 . The effect 1

of stretch ratio on the shrinkage o f

uniaxially oriented P m j i l m
1127

AND SCIWCE, JULY 1994, W. 3 , No. 14 4

Wayne K. Shih ented at a higher stretch ratio, such as 4 x 1 and above.

CONCLUSIONS
1. A model has been developed to quantlfy the ther-

REFERENCES
1. F. Rietsch, R A. Duckett, and I. M. Ward, Polymer, 20, 1133 (1979). 2. T. Pakula and M. Trznadel, Polymer, 26, 1011 (1985). 3. M. Trznadel, T. Pakula, and M. Kryszewski, Polymer, 26. 1019 (1985). 4. F. Rietsch, Polym. Bull., 15, 47 (1986). 5. J. M. Perena and R Benavente, Polyrn Eng. Sci., 28, 1260 (1988). 6. M. Trznadel and M. Kryszewski, Polymer, 29, 418 (1988). 7. G. Capaccio and I. M. Ward, Colloid Polyrn. Sci.,260. 46 ( 1982). 8. 0. Gal, D. Basic, and M. Petric, Shrinkage of Polymer

mal shrinkage behavior of polyester shrink film under isothermal and nonisothermal conditions. This model employs the straightforward first order reaction kinetics to an otherwise complex relaxation process. It offers three unique parameters for quality control and material specification of shrink film. These parameters can replace a complete shrink curve or tabulated shrinkage data. The model fits the experimental data very well. 2. The thermal shrinkage of several polyester homopolymers, copolymers, and polyester blends was investigated and compared to that of PVC shrink film. Two polyester blends containing PETG, Kodabond, and/or PET behave like PVC in shrinkage. 3. The stretch temperature greatly affects the ultimate shrinkage of uniaxially oriented PETG film. The high stretch temperature reduces the orientation and thus the ultimate shrinkage. The shrink curve but not the onset shrink temperature of PVC shrink film can be closely matched by adjusting the stretch conditions of PETG shrink film. 4. The effect of stretch rate on the shrinkage of PETG shrink film was not observed in the range from 5 to 20 in./s. 5. A higher stretch ratio is needed in order to obtain better thickness uniformity of the oriented PETG film.

f Materials and Memory Effect, in Integration o Fundamental Polymer Science and Technology, P. J. Lemstra and L. A. Kleintjens. eds., Elsevier, New York (1989). 9. A. M. Ghanem and R. S. Porter, J. Polyrn Sci: Part 3: Polyrn Phys. Ed., 27, 2587 (1989). 10. H. Kambe and T. Kato, Appl. Polyrn S y m , No. 20, 365
( 1973). 11. H. Kambe, T. Kato, and M. Kochi, J. Macroml. Sci.-Chem, As, 157 (1974). 12. Y. Tanabe and H. Kanetsuna, Polymer, 20, 1121 (1979). 13. J. W. Tobis and L. J. Taylor, J. Appl. Potym. Sci., 19, 1317 (1975). 14. D. M. B i g , Ado. Polyrn Techol., 10, 101 (1990). 15. M. Trznadel and M. Kryszewski, J. Macromol Sci.-Reu. Macromol Chern Phys., C32,259 (1992). 16. W. H. Press, B. P. Flannery, S. A. Teukolsky, and

W. T. Vetterling, Numerical Recipes, Cambridge University Press (1986). 17. M. Trznadel, Polymer, 27. 871 (1986). 18. W. K. Shih, Modeling the Shrinkage of Heat Shrinkable Film. to be published.

Receiued November 23, 1992

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POLYMER ENGINEERING AND SCIENCE, JULY 1994, Vol. 34, No. 14