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NBSIR 84-2989 (NASA) AlllOM DSn^E

The Structure and Properties of

Polyethylene Films Used In Heavy

Lift Balloons

Report for the Period

January-May, 1984

NASA Order S01834D

December 1 984

Issued March 1985

-QC100 EPARTMENT OF COMMERCE

.U56 AL BUREAU OF STANDARDS

8^-2989

198b

c. 2

NBSIR 84-2989 (NASA)

NATIONAL BUREAU OF STANDARDS

LIBRARY

The Structure and Properties of

Polyethylene Films Used in Heavy

Lift Balloons

. 0

I

F. Khoury

J.M. Crissman

B. M. Fanconi

H.L. Wagner

LH. Bolz .

C. A. Harding

Report for the Period

January-May, 1 984

NASA Order S01834D

December 1 984

Issued March 1 985

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

(i)

Abstract

The following features of five polyethylene films used by NASA in the

construction of heavy lift balloons have been examined: molecular weight,

molecular weight distribution, branching, melting behavior, density,

surface texture, birefringence, orientation of crystalline regions,

uniaxial deformation in the machine and transverse directions, and the

effect of sample geometry and strain rate on deformation behavior. The

goal of this exploratory study was to determine whether there are significant differences in any of the above mentioned features, or combination of features between the films. The acquisition of such

information is a first step towards determining whether there are any

specific correlations between film characteristics and the incidence of

catastrophic failure of balloons during ascent through the troposphere.

This exploratory study has resulted in the identification of similarities

and differences between various features of the films. Close similarities

have been found in methyl group content, crystallinity, and peak melting

temperature. The preferred orientations in the crystalline regions appear

to be qualitatively similar or related. Differences among the films have

been revealed in two features, namely between their molecular weights, and

in the balance of the strain to break behavior in the machine direction

relative to that in the transverse direction.
(ii)

Table of Contents

A. Introduction 1

B. Molecular Weight and Molecular Weight Distribution 2

(i) Dilute Solution Viscosity 2

(ii) Size Exclusion Chromatography (SEC) 2

C. Fourier Transform Infrared (FT-IR) Analysis of Methyl

Group Content M

D. Differences between Infrared Spectra of Films 5

E. Density Measurements 6

F. Differential Scanning Calorimetry (DSC) 6

G. Fine Structure and Orientation 8

(i) Fine Structure 8

(ii) Orientation 9

(a) Birefringence 9

(b) Wide Angle X-Ray Diffraction and

Infrared Spectroscopy 1

H. Mechanical Properties 15

(i) Creep Behavior 15

(ii) Elongation to Break, Tensile Strength, Yield

Stress 1

(iii) Effect of Strain Rate 18

(iv) Comparison of Tensile Properties of Different

Rolls of Category I Film 19

(v) Haziness 19

(vi) Wide Strip Geometry 20

(vii) Bubble Inflation 21 (viii) An Example of the Influence of Molecular

Weight and Molecular Weight Distribution on

the Tensile Properties of Polyethylene 21

I. Summary 23

J. Concluding Remarks 25

K. References 27

L. List of Tables 29

M. List of Figures 30
A. Introduction

The study described in this report was sponsored by the Balloon Projects

Branch of the National Aeronautics and Space Administration (NASA). It was carried out in the period January-April 198M as part of an ongoing

investigation by NASA to determine the causes of the catastrophic

failure of 'heavy-lift* balloons.

Helium filled heavy-lift balloons, in which the helium is contained by

low density polyethylene film, are used by NASA to raise instrument

payloads of up to -BOOOKg (gross inflation) to elevations of over 30Km

for various research projects. The thickness of the polyethylene film

is usually in the range 13um“25|jm. The capacity of the balloons at

float altitude can be as large as 1*16x10^ cu. meters. Since 1980 NASA

has experienced an increased incidence of catastrophic balloon failures

during ascent at elevations between 12Km-l8Km where the ambient temperature is The causes of the increased failures of this type from

1980 to the present as compared to the performance of balloons prior to

1980 have been elusive. Limitations inherent in the design characteristics of the balloons, inadvertent flaws which may occur in the process

of balloon assembly (construction), and differences between the mechanical properties of the polyethylene film used in the balloons prior to

and since 1980, are among the possible causes NASA is investigating.

The present exploratory study is concerned with the latter of these possibilities .

The mechanical properties of polyethylene films are governed by both the

molecular characteristics (molecular wt., molecular wt. distribution,

chain branching) of the polymer, and the film microstructure (e.g.

crystallinity, orientation of the crystalline regions etc.). The

microstructure is governed in part by the molecular parameters, and in

large measure by the processing conditions used in film production. The

details of the tubular film extrusion process (es) used in the production

of the films for the heavy-lift balloons are proprietary. Films must

meet various acceptance criteria set by NASA. An important empirical

criterion is that in uniaxial extension tests the extension to break in

the machine and in the transverse directions should not be less than

250? at -70°C.

The purpose of the short-term exploratory study described below was to

examine various features of the molecular characteristics,

microstructure, and mechanical properties of polyethylene films

representative of those produced and used in heavy-lift balloons prior

to 1980 and from 1980 onwards. The primary goal was to determine

whether there are significant differences in any of the above mentioned

features, or combination of features, between the films. Such knowledge

is clearly a necessary first step towards determining whether there are correlations between film characteristics not covered by present

acceptance criteria, and balloon performance.
2

The five low density polyethylene films studied were selected by NASA

and are identified as Category I to IV and B1 . Only the Category III was representative of film produced prior to 1980.

B. Molecular Weight and Molecular Weight Distribution.

Two types of measurements which are related to the molecular weight and

molecular weight distribution of the polyethylene in the films have been

carried out, namely (i) the determination of the viscosity of dilute

polymer solutions, and (ii) size exclusion chromatographic measurements.

( i) Dilute Solution Viscosity.

These measurements consisted in determining the flow times in a capillary viscometer at several concentrations of the polymer in

1,2,4-trichlorobenzene at 130°C, and extrapolating to zero concentration

to obtain a "limiting viscosity number" or intrinsic viscosity [n]. The

results for polymer taken from one sheet of film from each of the five

categories submitted by NSBF, as well as the pellets used to produce

Category B1 film, are given in Table 1

The precision in [n] is ± .01 -.02 indicating a small difference between

Categories I and IV on the one hand and Categories II and III on the

other. A much larger difference is observed between these four categories and the polymer of Category B1 both as film and pellets. These

limiting viscosity numbers cannot be directly translated into a viscosity average molecular weight by means of the Mark-Houwink relation

[n]=KM°^ (M=mol.wt., K and a are constants) because the polymer in the

films is branched polyethylene for which such a relation is inapplicable.

Two types of branching are usually present, long chain and short chain.

A branched polymer molecule of a given molecular weight will have a smaller hydrodynamic volume than a linear chain of the same molecular

weight, and hence a lower viscosity. Hydrodynamic

volume also determines elution volume in size exclusion chromatography.

Long chain branches are more effective in reducing hydrodynamic volume

than short chain branches. Hence, the extent and nature of the branching determines the magnitude of the effect on viscosity and elution volume.

( ii) Size Exclusion Chromatography (SEC):

In these experiments the polymer is separated into its constituents by

molecular size. For linear (unbranched) polymers this is equivalent to

obtaining the molecular length or weight distribution. In the case of

branched polymers such as the polyethylene in the films under study,

size is determined by branching as well as molecular length, thus making

interpretation of the chromatograms more complex.
3

The chromatograms were obtained with the Waters* Model 150C Liquid/Gel

Permeation Chromatograph containing five microstyrogel columns with

nominal pore size 10^, iq 3, 10^, 10^ and 10^ ^ , covering completely the

commercially available range of pore sizes. Runs were carried out at

135°C with purified 1,2,4 -trichlorobenzene as the eluant. Each solution contained about 0.255^ (w/v) of polymer to which 0.255 (w/v) Santonex*

antioxidant was added and was filtered through a 5utn Teflon* filter.

Calibration was carried out with Linear Polyethylene SRM 1475 as well as with eleven narrow molecular weight distribution polystyrene standards

using the universal calibration technique to give a calibration range of

850 to 4.6x10^ for linear polyethylene.

The chromatograms of the branched polyethylene in the five categories of

film indicated that the molecular size distributions are very broad and

extend beyond the accessible range of the columns. Since the polyethylene is branched the molecular weights very likely extend to greater than

about 5 million, depending on the amount and type (long and/or short) of

branching.

Calculations of molecular weight were carried out for polymer only

within the calibration range, and assuming the polyethylene is linear . These "apparent" molecular weights are given in Table 2. As already indicated the correct molecular weights are likely to be higher because

of the effect of branching and because extremely high molecular weight

material was excluded from fractionation by the columns; some of this

extremely high molecular weight material might include microgels, known

to occur in branched polyethylenes.

A method of calculating molecular weights of branched whole polymers,

requiring several assumptions, has been given in the literature [l]. It

is assumed that the extent of branching is independent of the molecular

weight of the species making up the distribution, an assumption which

would not be expected to be generally true and which has been shown to

be incorrect for low density polyethylene [2]. In addition the relationships used to derive the dependence of the number of branch points

on the radius of gyration [3] apply to a specific type of branching

which does not necessarily occur in low density polyethylene. For this

reason, and because the molecular weight range in the films extends beyond the limits of commercial columns, no attempt was made to use this

method to calculate "corrected" molecular weights or the extent of

branching.

Two separate size exclusion chromatography runs were carried out, each

at different times, requiring two calibrations of the columns.

In the first series of experiments (denoted A in Table 2) films of Category I through IV were compared. In the second series (B in Table 2)

designed to evaluate Category B1 film and the pellets from which it was produced, measurements on samples of Category I and III were repeated as

a cross-check with the first series. The apparent molecular weight values for both runs for the Category I and III films fall within the ex- pected error of the measurements. The chromatograms of all five

Categories of film are similar to one another, showing evidence of a

Certain coimiercial materials and equipment are identified in this paper in order to specify adequately the experimental procedure. In no case does such identification imply recommendation or endorsement by the National Bureau of Standards, nor does it imply necessarily the best available for the purpose.
4

bimodal distribution with a hint of a third peak. These features are likely the result of a blending of polymers. Upon comparing the normalized chromatograms, which have been superimposed in Figures 1-6, it is

evident that the Category III sample has a greater amount of high mo- lecular weight species than all the other samples. The sample of Category II also contains a greater amount of higher molecular weight

material than I, IV, and B1 , but less than category III. These differences are reflected in the molecular weight averages given in Table 2,

and are consistent with the limiting viscosity numbers of Table 1 , which

are higher for Categories III and II than those of Categories I, IV, and

B1 .

The Category B1 film and the raw polymer from which it was produced have

very similar bimodal distributions as shown in Figure 4. No great significance can be attached to the small differences at the peak. However

the size exclusion chromatography results, substantiating the viscosity

data of Table 1 , demonstrate a substantial difference between Category

B1 and the polymer from Categories I and III. Superposition of the nor- malized chromatograms in Figures 5 and 6 shows that Category B1 contains

less of the high molecular weight polymer than any of the others. It is

possible that this would also result in a smaller microgel content in

film B1 . On examination of the low molecular weight ends of the

chromatograms, not shown in the figures, no differences among the films were observed below a molecular weight of 1 ,000.

C. Fourier Transform Infrared (FT-IR) Analysis of Methyl Group Content.

Infrared spectroscopy provides an indirect measure of the degree of

branching in polyethylene chains through analysis of infrared bands attributable to methyl (-CH^) and methylene (-CH 2

-) groups. The presence

of methyl groups which occur at the ends of chains and at the ends of

the side branches attached to carbon atoms along the chains is di;^tinguished in IR spectra by an absorption band at 1 378 cm“"' . This band

which corresponds to the methyl deformation mode is assignable to methyl

group vibrations irrespective of the chemical bonding of the carbon atom

to which the methyl group is attached. The method of analysis which was used to compare the methyl group content of the films relative to one another is based on determining the ratio of the intensity of the re- solved 1378 “^ absorption band divided by the total integrated intensity

in the frequency range 1400 cm"^ to 1328 cm~^ , which, in addition to the

1378 cm~^ methyl band, includes bands that arise from wagging modes of

methylene groups in the non-crystalline regions of the polymers (see

later)

Single thicknesses of the films were too thin to yield spectra which

could be analyzed meaningfully for methyl group concentrations. Samples

composed of several layers of film were also not suitable owing to spectral effects arising from multiple reflection from the thin films. To

overcome these limitations samples were prepared by melting three layers

of each type of film in a press which was heated to 110°C and then

cooled to room temperature. This preparation procedure destroys any
5

orientation present in the original films, it is known however from previous work that the methyl group vibrations are not sensitive to orientation effects.

Spectra of the five categories of film in the frequency range 1400 cm~^

to 1328 cm“l are shown in Fig. 7. As indicated above the band at 1378

cm""* is assigned to the methyl group and the remaining bands in the figure arise from the methylene wagging mode in the non-crystalline regions

of the film. The complex band shapes exhibited by the spectra were

decomposed into individual components using the method of Rueda, BaltaCalleja and Hidalgo [4], and the value of the intensity of the resolved

1378 cm""’ band divided by the total integrated intensity from 1 400 cm""' to 1328 cm""' was determined for each film. The resulting ratios for the

five categories .of film are listed in Table 3 from which it can be seen

that they are approximately the same for all five films. In short there

is no appreciable difference in methyl group content between the films.

Using the following empirical relationship developed by Rueda et al [4]

E= ( 0 . 085 ) K-j g — 0.09

(where E is the number of methyl groups per 100 carbon atoms in the

polyethylene, K.| is the resolved intensity of the 1 378 cm"^ methyl

band per unit thickness of the film in cms) and assuming that the molten

and pressed films were all approximately 2.4 mils (6.1xlO~3 cm) thick,

it is estimated from the data in the third column in Table 3 that the

methyl group content in the films is ^2.1 methyl groups/100 C atoms.

( D) Differences between Infrared Spectra of the Films.

Although the FT-IR room temperature spectra of the samples of the five

film categories taken after melting, pressing, and cooling (see previous

section) were essentially similar to one another in the frequency range

1328-1400 cm~^ , differences between the spectra of these samples were

observed at other frequencies in the mid-frequency range 400 cm~^ - I 800

cm"^ . Thus, the B1 film exhibited two prominent absorption peaks at 471

cm~^ and 1085 cm“^ which were not observed in any of the Category I-IV

films. The difference spectrum obtained by subtracting the spectrum of

the Category I sample from that of Category B1 is shown in Fig. 8. In

addition to the two prominent bands mentioned above weak absorption

bands are found at 613 , 671, and 792 cm””' . No other significant differences between these two films were observed in the frequency range

400-4000 cm""' .

The spectral pattern exhibited by the difference spectrum in Fig. 8 does

not correlate with any known absorption bands for polyethylene which

suggests that the prominent absorption bands at 471 cm“^ and 1085 cm""' as well as the three weaker bands mentioned above are due to the presence of a rather high concentration of additive (or additives) in the B1

film. Although the differential scanning calorimetry experiments re- ported in Section (E) indicated the presence of an additive (or additives) in the B1 as well as in the Category I-IV films no distinguishable evidence of absorption bands at 471 cm"^ and 1085 cm"^
6

was detected in the spectra of the latter four films. The occurrence of

two weak absorption bands at 1150 cm“^ and 1723 cm~^ in the spectra of

Cat. I-IV films may be attributed to another type of additive or additives since these latter spectral features are also not characteristic

of polyethylene.

E. Density Measurements.

The density of each of the five categories of film was determined at 23

± 0.1 °C using water/ethanol density gradient columns. Appropriate precautions were taken to deaerate the samples prior to immersion in the

columns. The results obtained for two samples from each film type are listed in Table 4. The corresponding weight % crystallinities, x> are listed in the same Table. They were calculated from the following ex- pression:

(p-p^)

X = 100 — . 7

r p (P^-P^)

where p is the measured density of the sample, p^ is the density of

purely crystalline polyethylene (i.e. the unit cell density), and p^ the

density of amorphous polyethylene. The values used for p^ and p^ were

1.000 g/cc [5] and 0.85^7 g/cc [6] respectively.

As can be seen from the data in Table 4 the two measurements carried out

on each category of film are in good agreement with one another (within

the experimental error of <±0.0005 g/cc), and any differences in density

between the films are extremely small. It appears from these data that

the Category B1 film is slightly denser than the other four types, and

that the Category II film may be marginally denser than the Category I,

III, and IV.

F. Differential Scanning Calorimetry (DSC).

A specimen from each of the Category I to IV films listed in Table 1 and

the B1 film was heated at a constant rate of 20°C/min from -40°C to

120°C in order to determine the peak melting temperature. The samples were then cooled from 120°C at 20°C/min to below room temperature to determine the location of the peak crystallization temperature. The re- sults of DSC experiments are affected by the heating and cooling rates

used, hence data obtained at only one rate are not absolute. The main

objectives of the present exploratory experiments using a single heating

and cooling rate was to determine whether there exist significant relative differences between the peak melting temperatures and/or the peak

crystallization temperatures exhibited by the films. Large differences

in peak melting temperatures can be expected to occur, for example, if

the thermal and stretching conditions used in the production of the

films differed appreciably, and/or if the molecular characteristics (molecular weight, branching) of the starting polymers are significantly
7

different from one another. Differences of the latter type might also

be reflected in differences in the location of the peak crystallization

temperature exhibited by the molten specimens upon cooling.

In the heating experiments, film of all five categories exhibited two

melting endotherms, namely a very weak one peaked at a temperature below

60°C, and a very pronounced one peaked in the narrow temperature range

106.2°C-107. 1 °C. The latter endotherm is due to the melting of the bulk

of the polymer in the films. The temperatures corresponding to the peaks

of the low and high temperature endotherms for each film are listed in

Table 5.

In the cooling experiments all the films exhibited two crystallization

exotherms. A very pronounced exotherm, due to the crystallization of

the bulk of the polyethylene, and having a peak temperature in the narrow range 93.0°C to was observed in each case. In addition, a very weak lower temperature exotherm peaked in the range 53.6°C-58.4°C,

was recorded in all the films. The temperatures corresponding to the

peaks of the high and low temperature exotherms for each film are listed

in Table 5.

The normalized (to a specimen wt. of 1.0 mg) DSC curves exhibited by the

Category I-IV films upon heating and cooling are illustrated in Figs.

(9-1 2) a and (9-1 2) c respectively in which the low temperature melting

and crystallization peaks are barely if at all visible. The occurrence

of these peaks is evident however in Figs. (9-1 2)b and Figs (9-1 2)d in

which parts of the heating and cooling curves are respectively shown

with the vertical scale expanded by a factor of six. The heating and

cooling DSC curves for the B1 film are shown in Fig. 13a and Fig. 13b

respectively.

The DSC experiments described above show that there are only slight differences between the main (high temperature) peak melting temperatures

and between the main peak crystallization temperatures exhibited by the

Category I-IV and Bl film specimens. The experiments also show that all five

films contain a small amount of material which melts and crystallizes at

much lower temperatures than the bulk of the polymer in the films. The

nature of this material(s) is not known, it is however reasonable to

speculate that it may be additive, the presence of which in these films

was already suggested in Section D in which it was pointed out that infrared spectra of the five films exhibited absorption bands which are

not characteristic of polyethylene. The infrared spectroscopy observations also suggested that the additive in the Bl film is different from

that in the Category I-IV films.

As can be seen from Table 5 the weak peak melting and crystallization

temperatures of the presumed "additive” material occur within the range

47°C-59®C. It should be noted in this connection that there is considerable overlap between the temperature ranges spanned by the low temperature endotherm and the exotherm exhibited by each film. It is

nevertheless surprising at first glance that the low temperature melting

peak manifests itself at a lower temperature (47.8 °C-54.4°C) than the
8

low temperature crystallization peak (53*6°C-58. 4°C) . Whether this is

due to a redistribution, during the heating cycle, of the additive in

the covered specimen chamber (pan) in the DSC apparatus remains an open

question, as does the observation that when the samples were subjected

to a second heating cycle no evidence of the low temperature endotherm

was observed in the Category I, III, IV and B1 films, however upon being

cooled again to below room temperature from 120°C all five films exhibited a low temperature exotherm.

( G) Fine Texture and Orientation.

( i) Fine Texture

All the films (Category I-IV and B1 ) appear hazy to the naked eye. When

examined in transmission with a light microscope using phase contrast

optics they all exhibit a mottled appearance on a fine lateral scale (a

few micrometers) as shown in Figures (14-1 8) a. This appearance may be

due to differences in internal fine structure and hence refractive index

between the brighter and darker regions seen in Figs. (1 4-l8)a and/or due

to differences in film thickness in these regions. In order to determine whether this appearance of the films is associated with variations

in the thickness of the films on a small lateral scale_,replicas

(imprints) were made of the two surfaces of a specimen of each of the

five types of film. The specimens were taken from the same rolls

(gores) listed in Tables 4,5. The replicas were made by applying a con- centrated solution (10?) of nitrocellulose in amyl acetate to the surfaces of the films and allowing it to dry at room temperature. The

resulting nitrocellulose replicas were stripped from the surfaces and

examined in transmission in a light microscope using phase contrast optics. If the surfaces of the polyethylene films were perfectly smooth

the replicas would appear featureless. This was certainly not the case,

as illustrated in Figs. ( 14-l8)b and (14-l8)c in which it can be seen

that the replicas exhibit fine textural appearances akin to the actual

films in Figs. ( 14-I3)a. This confirms the occurrence of variations in

film thickness on a small lateral scale (i.e. over distances of a few

urn) in all the films thus indicating that the haziness of the films is

due, in part at any rate, to the surface roughness of the films. Surface roughness in blown films is not an uncommon feature (e.g. see references [7,8]). A scanning electron micrograph of one of the sur- faces of the Category I film is shown in Fig. 19 in which the uneven

character of the surface is directly evident.

The Category B1 film could be distinguished from the other four types of

film in the optical microscope (with either normal or phase contrast optics) by its high content of dispersed particles of different sizes and

shapes. With phase contrast illumination they appear as very bright objects. Several such objects can be seen in Fig.l8a (features denoted X)

The occurrence of the particles in the replicas (Figs. I8b,c) of both

surfaces of the film indicates that many of the particles are situated

on these surfaces or are partially embedded in them and hence easily ex- cised. Whether these objects are particles of the additive detected by

infrared spectroscopy (see Section D) is not known. A consideration
9

which should be borne in mind is that embedded or partially embedded

particles can give rise to uneven stress distributions in a film undergoing deformation and could thus influence the mechanical characteristics of the film.

Differences in haziness to the naked eye were observed between adjoining

regions in some portions of the Category I, II and IV films. The diffuse demarcation "line” between the regions which appeared hazy and less

hazy was parallel or closely parallel to the machine direction and extended over the length of the samples submitted by NASA. The hazy and

less hazy regions exhibited similar appearances when examined under the

light microscope using phase contrast optics.

( ii ) Orientation

For the sake of brevity in describing the results of an examination of

the birefringent characteristics of the films as well as the results of

wide angle x-ray diffraction experiments and infrared spectroscopy we

shall refer to the machine and transverse directions as M and T respectively, and to the direction normal to the surface of the films (i.e.

normal to the MT plane) as N. In addition the refractive indices for

light travelling parallel to N and polarized with its plane of vibration

parallel to M or parallel to T will be denoted n(M) and n(T) respectively.

(a) Birefringence

The birefringent character of oriented polyethylene films is determined

by the distribution of the orientation of the crystalline regions in

them, by the film crystallinity, by any optical anisotropy (orientation)

in the disordered ('amorphous’) regions, and by form birefringence [9].

As pointed out in Section E the crystallinities of the five films are essentially equal. In the absence of any knowledge of the conditions

under which the tubular films are extruded (rate of cooling, draw ratio,

blow ratio), it can be reasonably presumed, as a starting premise, that

the birefringence in the films is due predominantly to crystalline orientation. The birefringence in the MT plane of the films was examined

to determine whether there are significant differences between them,

i.e. in both the sign (±) of An=n(M)-n(T) relative to M and the magnitude of An on a scale of 0-0.06 [10]. As background concerning the upper limit of this scale the following may be noted. The unit cell of

polyethylene is orthorhombic [5]. Its parameters are a=0.?4nm,

b=0.493nm, c=0.254nm, a=B=Y=90°. The chain molecules are parallel to

the c-axis. It is commonly assumed, to a good approximation, that the

refractive indices of the unit cell are the same as in single crystals

of orthorhombic normal-paraffins (e.g. n-C25HYi|[ 1 0]) and that n^=1.5l4,

n^j=1519, and n^,=1 .575 [11]. If one imagines a single crystal of polyethylene oriented relative to the film with the b-axis parallel to N and

the c and a axes parallel to M and T respectively, the crystal would ex- hibit maximum birefringence, n^-n^ =0.06, in the MT plane and be positively birefringent with respect to M. In reality, of course, films

consist of microcrystalline regions interspersed with disordered regions
10

which in the case of the films under consideration amount to slightly

more than 50^ of the weight of the films (Section E). Furthermore the

preferred crystal orientation distributions commonly encountered in

blown films differ from the idealized example given above [see Section

G(ii)b]. Thus, the birefringence of the films in the MT plane would be

expected to be less than 0.06.

Specimens of the five films were examined between crossed polarizer and

analyzer with an optical microscope using parallel illumination. The

specimens, which lay flat on the microscope stage (i.e. MT plane parallel to the plane of the microscope stage and perpendicular to incident

light beam), were cut from the same rolls (gore) as those listed in Table 1. Examination of the extinction characteristics of the various

specimens revealed from the outset a distinct difference between the

Category I, II, IV and B1 specimens as compared to those of the Category

III (roll #112858, Core 177). The former four types of specimens exhibited extinction when the nominal machine direction M (based on the inked

identification on the films) was parallel or closely parallel to the

plane of vibration of the polarizer. In addition, using a first order

red retardation plate it was established that in these four types of

specimens n(M)<n(T). The magnitude of the birefringence

An=n(M) -n(T)=Y/t (where Y is the retardation and t the thickness of the

specimens), was determined using a Berek compensator to measure Y. The

film thicknesses quoted by the manufacturer were assumed. In each case three specimens approximately 4cm x2cm were cut from different parts of

a 10cm X 15cm sheet of film and the birefringence in three different re- gions of each 4cm x 2cm piece was determined. The area sampled in each

measurement was -Imm^. As can be seen from the results listed in Table 6

n(M)<n(T) for Categories I, II, IV and B1 with An ranging from -0.0012

to -0.0019.

In contrast with the four films mentioned above, specimens of the Category III film, roll #112858 (Core 177 excised from the W41.47 balloon)

exhibited considerable differences in their extinction characteristics.

Extinction between crossed polarizers was observed with the angle 0 between the machine direction and the plane of polarization of the

polarizer varying from 0° to 40°. A first order red retardation plate

was used to determine that in all these areas n(M) was greater than n(T)

(i.e. An was positive) in contrast with the other four films. Furthermore the birefringence was found to be extremely weak in the samples

which exhibited extinction at angles 0 ^30 between M and the plane of

polarization of the polarizer. The birefringence of six areas which ex- hibited extinction at 0 in the range l4°-29° were very close to one another, (+0.0005 to +0.0007). It should be emphasized that the latter

birefringences do not represent differences between nj^^j and n-p but represent the difference in refractive index for light polarized parallel and

perpendicular to the direction of extinction.

In order to see whether the extinction and birefringence characteristics

of the Cat. Ill roll #112858 (Core 177) were peculiar to that gore, several areas of roll 111958 (Core 121) from the same balloon were examined. They exhibited similar variations in extinction direction as
11

those described above. Similarly, n(M) was also greater n(T). The evident question which arose was whether the features described above,

which distinguished the type III specimens excised from gores 177 and

121 from the specimens of the four other films, are characteristics of

the Type III film as made, or are a consequence of handling e.g. during

the manufacture of the balloon. The possibility that 'handling' might be

the reason is suggested by an examination of specimens of Type III (roll

#112877) film which had not been incorporated in a balloon. Film from

the same roll had been used in one of the gores (#146) of the balloon

from which specimens 112858 (Gore 177) and 111958 (Gore 121) originated.

The specimens of roll #112877 exhibited extinction when the nominal machine direction was parallel to the plane of polarization of the

polarizer. Furthermore n(M) was less than n(T) as is the case in the

other four Categories of film. Measurements of birefringence, as car- ried out on the other films, yielded the result listed in Table 6

(An=-0.0011) which, although lower, seems to be more in keeping with the

optical character of the other four films.

As pointed out in Section G(i) there are differences in haziness in different regions of the Category I, II and IV films and the demarcation

line between the hazy and less hazy regions in the films runs closely

parallel to the machine direction. Some additional birefringence measurements were therefore taken to examine whether there are substantial

differences in birefringence between the differently hazy regions in

each film. The measurements were made at successive 3nim intervals away

from the demarcation line between the regions. The results are given in

Table 7.

Neglecting the results for the Category III (#112858, Gore 177) specimens in the light of the measurements on virgin Category III (#112877)

film, there are two features of the data in Table 6, 7 which stand out.

(1) All the films exhibit negative birefringence relative to M. (2)

The magnitudes of the birefringences, which are in the range-[0. 0009 to

0.0019], all fall at the lower end of the birefringence scale 0-0.06

mentioned earlier, and correspondingly any differences in An between the

films are small relative to that scale.

Because of (1) the limited samplings used in the measurements, (2) the

assumption that the thickness of each specimen was uniform and equal' to

the nominal thickness quoted by the manufacturers, and (3) the overlap

between the An values obtained from the different films, it is not possible to derive any definite conclusions regarding differences in An between the films or between the hazy and less lazy regions in the

Category I and II films. The data suggest that the magnitude of An may

be smallest in the Category III film. It remains an open question however whether this observation, and e.g. the apparent differences between

An in the hazy and non-hazy regions in the Category I and II films [Table 7] which are the opposite in the Category II film compared to I,

would stand up to measurements on very much larger populations of samples. The same consideration applies to the deviation of the extinction

position from M exhibited in the vicinity of the interface between the

hazy and less hazy regions in Category II film (Table 7). Additional
12

comments on the birefringence exhibited by the films are included in

Section I in conjunction with the results of the wide angle x-ray diffraction and infrared spectroscopy on the orientation of the crystalline

regions in the films.

(b) Wide Angle X-ray Diffraction and

Infrared Spectroscopy

As pointed out in the previous section blown films of polyethylene consist of microcrystalline regions interspersed with disordered regions.

The microcrystals adopt different preferred orientations relative to the

M, T, and N directions depending, inter alia, on the rate at which the

tubular extrudate is cooled, and on the stretch and blow ratios imposed

on it [see e.g. refs. 12-15].

As background to the wide angle x-ray diffraction (WAXD) experiments reported in this section it should be pointed out that the quantitative

characterization of the crystalline orientation in films requires; (1)

The determination of the preferred orientation of the a,b, and c-axis of

the microcrystals relative to the M, N and T axes in the films. A possibility which may occur, and which should be borne in mind in this con- nection, is that a given set of processing conditions may yield a film

having e.g. two populations of microcrystals having distinctly different

preferred orientations relative to M,T, and N; (2) The determination of

the distributionC s) or deviations from the preferred orientation( s)

among the total population of microcrystals.

Tasks (1) and (2) outlined above require the determination of pole figures [16] which involves the monitoring of the changes in intensity

which key reflections undergo when the orientations of the M, T and N axes in the film sample are changed systematically relative to the incident x-ray beam by small angular increments over wide angular ranges.

These tasks can be achieved with an automated counter x-ray

diffractometer having a four circle goniometer sample holder and

equipped with data collecting, processing and display facilities. Such

a system, which is currently being installed in the Polymers Division,

was not available during the period covered in this report.

In the comparatively limited exploratory experiments described below, a flat plate camera set-up was used to record photographically the diffraction patterns exhibited by each type of film when it was oriented in

three different ways relative to the collimated beam of monochromatic

x-rays (Ni filtered CuKa radiation), A=0. 1 5^l8nm) . The three orientations were with the T, the M and the N axis of the film set parallel to

the incident x-ray beam respectively. For the sake of brevity the cor- responding diffraction patterns will be referred to below as the T, M

and N patterns. The patterns obtained from the five films are shown in

Figs. 20-24. The orientations of the two orthogonal axes in the polyethylene film which lie in the plane normal to the x-ray beam are identified in each pattern (e.g. the M and N axes in the T diffraction

patterns etc.). The most evident reflections exhibited in all the patterns are (in order of decreasing intrinsic as well as observed intensity) the 110 the 200 and the 020 reflections. The interplanar spacings
13

corresponding to these reflections are 0.4lnm, 0.37nm and 0.246nm [5].

These reflections which are identified in all the patterns (Figs. 20-24) occur as arcs which in some cases (particularly the 110 reflections) ex- hibit considerable azimuthal spread and appear ringlike in character.

An overall feature of the results of the experiments outlined in the

previous paragraph is the similarity in the dispositions of reflections

(relative to the film reference axes) between the T, between the M, and

between the N diffraction patterns of all the films. The following

characteristics may be listed in this connection:

T-diffraction patterns, Figs. (20-24)a

020 reflections: arcs spread preferentially about the axis parallel to

N

200 reflections: arcs spread preferentially about the axis parallel to

M.

110 reflections: two pairs of diametrically opposite arcs spread

about ± 30° from N

M-diffraction patterns, Figs. (20-24)b

020 reflections: arcs spread preferentially about the axis

parallel to N

200 reflections: arcs spread preferentially about the axis

parallel to T

N-diffraction patterns, Figs. (20-24)c

020 reflections: faint arcs spread preferentially about the axis

parallel to T

200 reflections: arcs spread preferentially about the axis

parallel to M

The arced or ringlike character of the various x-ray reflections exhibited by the films indicate that there are broad distributions in orientation about some preferred orientation or orientations. The preferred

dispositions exhibited by the 200 reflections in the M, T, and N diffraction patterns indicate that the microcrystalline regions in the

films are oriented with the a-axis preferentially parallel to the MT

plane and with a preference parallel to M. The dispositions of the 020

reflections suggest the b-axis is preferentially oriented parallel to

the NT plane and with a preference parallel to N.

A possible working model which suggests itself, and which would be con- sistent with the preferred a-axis and b-axis orientations indicated

above, is one in which the film is envisaged as containing mainly two

populations of microcrystals whose respective orientations are distrib-
14

uted preferentially about the two idealized orientations depicted in

Fig. 25. In Fig. 25a the tnicrocrystals are envisaged as being oriented

with the b-axis parallel to N and with the a-axis and the c-axis ran - domly oriented in the MT plane. In the case of Fig. 25b the

microcrystals are oriented with the a-axis parallel to M, and with the

b-axis and the c-axis randomly oriented in the NT plane. Preferred orientations corresponding to those in Fig. 25a and Fig. 25b would each ex- hibit T-dif fraction patterns in which the preferred dispositions of the

020, 200 and 110 reflections relative to the N and M directions are the

same and would correspond to the actually observed dispositions of these

reflections in the T diffraction patterns exhibited by the films which

were described earlier.

While the qualitative observations described above have identified features of the M, T, and N diffraction patterns which indicate that the

crystalline orientationC s) in the five films are similar or related in

type, more detailed studies using the automated counter-diffractometer

technique mentioned earlier will be necessary to compare their orientation characteristics (preferred orientations and orientation distributions) quantitatively, and to test the suggested working model.

Information on the orientation of the crystalline regions in polyethylene can also be obtained from infrared (IR) spectra. The methylene

rocking vibration of crystalline polyethylene gives rise to a doublet

the lower frequency (719cm~^) component of which absorbs IR radiation

polarized parallel to the b-crystallographic axis, while the higher frequency (733cm“^ ) component absorbs radiation polarized parallel to the

a-axis [17]. A complicating factor is that absorption near 719cm~^ may

arise from -CH 2 rocking vibrations in the disordered (non-crystalline)

regions of polyethylene. This complication notwithstanding, infrared

spectra of a sample from each of the five films were recorded with the

incident IR beam parallel to N in the films. Two spectra were recorded

in each case, namely with the incident beam polarized either parallel or perpendicular to the M direction (or the extinction direction nearest to

M) .

The -CH2 rocking region of the spectra exhibited by each film is shown

in Fig.26(a-e) in which it can be seen that the intensity of the 733

cm~^ band (a-axis) is always higher when the IR radiation was polarised

parallel (dashed line) to M as compared to perpendicular (continuous

line) to M, and that the reverse is true for the 719cm“^ band (b-axis).

The ratio of the intensity of each band for the two different

polarizations is listed in Table 8. It was pointed out earlier that absorption near 719 cm“^ may also arise from -CH2 rocking vibrations in

the disordered regions. Any orientation in these regions will also affect the intensity ratio of the 719 cm~^ band, and could account for the

differences between the parallel/perpendicular (733 cm~^ ) and perpendicular/parallel (719 cm“^ ) ratios exhibited by some of the films (Table

8). The data are nevertheless consistent with the wide angle x-ray diffraction patterns obtained with the x-ray beam parallel to N (N diffraction pattern) which indicated that in the MT plane there is a
15

preferential orientation of the a-axis parallel to M and the b-axis parallel to T (the 200 and 020 arcs are centered about M and T respectively, as pointed out earlier).

( H) Mechanical Properties

( i ) Creep Behavior (Categories I-IV)

As background to the investigation of the tensile elongation and tensile

strength at break of the films, the tensile creep behavior of the Category I-IV films was examined at 23±0.5°C for specimens which were cut

both parallel and transverse to the machine direction. The specimens

were cut with a die which conformed closely with the type (II) tensile

bar specified in ASTM 0638. In order to determine the strain as a function of time fiducial marks were placed approximately five centemeters

apart on the straight gage section of each specimen and the separation

of the marks was monitored with a cathetometer . The duration of each

creep experiment was generally about one hour.

In the first set of experiments the specimens were subjected to an applied engineering stress of 2.5 MPa (363 PSI). This level of stress

corresponds to about one fourth of the yield stress for these films as determined in uniaxial extension at a constant rate of strain (discussed

in a later section). The results are shown in Figure 27 plotted as log

strain versus log time. Under the conditions just described the maximum

strain after one hour was 2.2$ or less. No significant differences in

creep behavior occurred between the machine and transverse directions,

nor was there any appreciable difference in behavior from film to film.

Most of the observed differences are probably within the experimental

errors which can arise from factors such as nonuniformity in the film

thickness and creases due to folds which can result in uncertainty in

determining the initial unloaded gage length 2,^.

A second set of creep experiments was done using a larger applied engineering stress of 10 MPa (1450 PSI) which is very close to the yield

stress for these films at 23° (see later, Table 12). From Figure 28- it can be seen that at the higher level of stress, strains of from 30$ to

100$ were observed after about one hour. After one minute all of the

film specimens except two exceeded the strain at the yield point which

is in the range from 18 to 22$ for these films at 23 °C. Beyond the

yield point significant differences occurred between the machine and

transverse direction as well as from film to film. The Category I film

appears to be the most nearly balanced of the four films, and the Category IV film the least. Of the four films the Category II film exhibited the least amount of creep in the machine direction after one hour.

(ii ) Elongation to Break, Tensile Strength, Yield Stress

(Categories I-IV, B1 )

The tensile elongation and tensile strength at break of the Category

I-IV, and B1 films were investigated at 23±0.5°C and at -70±2°C. Due to

the limited amount of actuator travel available in our hydraulic test
16

machine fitted with a low temperature chamber, it was found necessary to use specimens which had a gage length of no more than about 1 to 1 .5 cm. Specimens were cut with a dumbbell shaped die specially designed so that

the ends widened rather gradually in the first 0.1 -0.2 cm beyond the

straight portion of the dumbbell. The straight portion of the dumbbell

was 0.80 cm long and the width in that narrow section was 0.315 cm.

For the initial set of experiments, which were carried out at 23±0.5°C,

the gage length was set at 1.0 cm so that at each grip about 0.1 cm of

the exposed gage section was slightly wider than the 0.80 cm long

straight section. The results of tests carried out on the Category I and II films are presented in Table 9. The values obtained were found

to be significantly smaller than those quoted by either the film manufacturer or the NSBF. Therefore much effort was devoted to examine the

effect of different specimen geometries and clamping arrangements on the

measurements. This effort involved the testing of approximately 200

specimens having geometries which varied from straight strips of different length to width ratios to the dumbbell shaped specimens described

above in which the gage length was varied. Of the different geometries

examined the one which consistently yielded in the greatest strain at

break was one using the original dumbbell shaped specimen gripped such

that only the straight section of the dumbbell was exposed between the

grips. Accordingly, all subsequent tests at 23°C and -70°C were carried

out using specimens with a gage length of 0.60 cm so that the length to

breadth ratio was 1.9, which compares to a value of 2 used by the NSBF.

The specimen grips were made of aluminum. They were covered with one

layer of a soft cloth electrical tape to prevent contact of the polyethylene film with the metal. Use of the cloth tape results in greater values of the strain at break. The rate of clamp separation, which was limited by the number of positions available on the function generator

of our testing machine, was set so that the specimen was strained at a rate of 991^ per minute as compared to a rate of 1000^ per minute used

by the NSBF.

Using the test procedures just described, the tensile properties of the

Category I-IV, and B1 films were examined at 23±0.5°C and the results

are shown in Table 10. In the machine direction the average strain at

break does not differ greatly among the five films, whereas in the

transverse direction significant differences do occur. For the Category

I and B1 films the average strain at break is slightly greater in the

machine direction than in the transverse direction. The reverse is true

for the Category II, III, and IV films for which the transverse direction exhibits significantly greater strain before failure. It should be

noted that the Category I-IV films exhibited a distinct maximum in the

stress-strain curve at low strains (range 18-2256) when stretched in the

transverse direction. A barely perceptible maximum occurred in the B1

film. None of the films exhibited a maximum in the stress at low

strains when stretched in the machine direction. Based upon the tensile

tests, the Category I-IV films are all consistent with the creep measurements described earlier where the specimens from these films subjected to a stress of 10 MPa (Fig. 28) were found to creep significantly

more in the transverse than in the machine direction, except for the
17

Category I film which exhibited more balanced behavior and also exhibited slightly higher creep in the machine direction than in the transverse direction.

The maximum and minimum values of the strain at break at 23°C are listed

in Table 11 for each of the five films. For stretching along the ma- chine direction the smallest minimum values occurred in the Category III

and IV films, whereas for stretching along the transverse direction they

occurred in the Category I and B1 films.

A summary is presented in Table 12 of the yield stress data obtained

from the same tensile tests described above. In the present work the

yield stress was defined to be either the point at which the

stress-strain curve went through a maximum (transverse direction), or if no maximum occurred (machine direction) it was taken to be the point at

which the stress-strain curve exhibited a sharp bend. The maximum average yield stress occurred for the Category I film in the machine direction and the minimum average value occurred for the Category III film in

the transverse direction. However, there did not appear any large

variation in yield stress among any of the five films at 23°C. For all

five films the strain at the yield point was in the range from 18 to

22 %.

Similar tests were carried out at -70°C on specimens cut from the same

sheets of film used for the 23°C tests. The results are summarized in

Table 13- The temperature control of the low temperature chamber was such that the actual specimen temperature at the time the test was started is estimated to be -70±2°C. To ensure that the specimen temperature was at least as low as -70°C, the chamber was initially cooled

to between -75 °C and -80 °C. The chamber was then warmed up to about

-71 °C and held at that temperature for several minutes. The test was generally started when the temperature in the vicinity of the specimen

was between -71 °C and -70°C. The temperature in the vicinity of the

specimen was determined by both a copper-constantan thermocouple placed

just below the specimen and a solid state device placed just above the

specimen.

As was the case at 23°C the Category II, III, and IV films exhibited

smaller average strains at break in the machine direction than in the

transverse direction, while the Category I film exhibited greater average strain in the machine direction. In the case of the B1 film however

the strain to break was larger in the transverse than in the machine direction, whereas the reverse occurred at 23°C. The average strains to

break in both directions are less for all five films at -70°C than they

were at 23°C, by about 33 percent overall. The standard deviations are,

however, much larger at -70°C than at 23°C, particularly in the case of

the Category II film. For the five sets of film samples examined, the

average strain at break in each case did exceed the current minimum re- quirement of 250% stipulated by NSBF, although in several cases individual specimens failed at elongations well below this value.
18

Table 14 shows the maximum and minimum values of the strain at break

corresponding to the data presented in Table 13- While in each case

the average strain at break exceeded 25055, each film, with exception for

the Category III film, exhibited at least one specimen which failed at a strain less than 250/5. One specimen of the Category III film exhibited

the largest elongation (60955) at -70°C of any of the specimens tested.

Table 15 presents a summary of the yield stress data obtained at ~70°C.

A comparison of the data in Tables 12 and 15 shows that at -70°C the

yield stress is from 4 to 5 times greater than it is at 23°C. Whereas

at 23°C the variation in yield stress from film to film was less than

I 255, at -70°C it is as much as 3755 . On average, the Category I film ex- hibits a higher yield stress than do the other three, while the Category

II film in the transverse direction exhibits the smallest average yield

stress. At the same time the strain at the yield points exhibited by

the films decreases from the 18-22? range at 23°C to the 6-9? range at

-70°C. It should be noted that all the films exhibited a maximum in the

stress strain curve at -70°C when stretched in the transverse as well as

in the machine direction. This contrasts with the deformation at 23°C

where the manifestation of a maximum occurred only upon stretching in

the transverse direction.

Using the data for the 64 specimens of Category I-IV and B1 filmswhose

properties are summarized in Table 13, we have plotted in Figure 29 the

strain at break versus yield stress at -70°C. Of the eleven specimens

which failed at a strain of less than 250?, 4 belong to Category II,

three to Category B1 , two to Category I, and two to Category IV. The

two smallest values obtained (46 and 72?) were from Category II. Of

these eleven specimens which failed at less than 250? strain, all but one exhibited a yield stress of less than 50 MPa. However, the overall

average yield stress for all 70 specimens tested was only 47.0 MPa (6831

PSD

(iii) Effect of Strain Rate.

Another aspect of the low temperature deformation of the films which is

of interest is the extent to which the ultimate tensile properties depend upon the rate of strain. The strain rate dependence was examined

at -70°C for the Category I, II, and B1 films and the results are pr-esented in Table 16. The strain rate was varied by a factor of one hundred, the lowest rate being 99.1? per minute and the highest being 9910?

per minute. It can be seen from Table 14 that in the range of strain

rates examined there is little, if any, dependence of the strain to

break on the strain rate. Except for the Category B1 film, at each rate

of strain the trends are the same as those found earlier. The Category

I film extends more in the machine direction than in the transverse direction while for the Category II film the opposite is true. The Category B1 film at the lowest and highest rate of strain shows the opposite

behavior to that at the rate of 991? per minute. At all three strain

rates each of the three films meets the minimum requirement of 250?

elongation, although Category I and B1 films do so marginally. Examination of the results on tensile strength indicates that, if averaged over
19

all three films, the average stress at break is slightly higher at a rate of 991$ per minute than at the other two rates, however the averages for the two extreme rates of strain are based upon the testing of

only three specimens cut along each direction.

( iv) Comparison of Tensile Properties of Different Rolls of Category

I Film

Following the tensile tests described earlier in this report on roll

315477 of the Category I film, several additional pieces of Category I film from roll 315421 were received from the NSBF which were cut from

areas very near those tested previously by them. The pieces were identified as Sample 2, areas 106-112. We have examined the tensile properties of specimens cut from the two areas identified as 107 and 111 and

the results are presented in Table 17. For comparison the results from

the earlier tests on roll 315477 are also included. The values quoted

represent averages for only three specimens cut in each direction for

areas 107 and 111, whereas for roll 315477 the averages are for six

specimens.

At both 23°C and -70°C the strain at break is greater for roll 315421

than for roll 315477, while the yield stress is greater for roll 315477.

Moreover, there appear to be differences in all three tensile properties

between areas 107 and 111 from roll 315421. At -70°C one specimen from

area 107 failed at a strain of less than 250$ (202$), whereas none from

area 111 failed at less than 380$ elongation. Also, at -70°C the specimens from area 111 cut along the transverse direction exhibited the

highest tensile stress at break of any of the five film categories

tested in this study.

( v) Haziness

As pointed out in Sections G(i) and G(ii)a films of Category I, II and

IV exhibit regions which to the eye appeared to vary in haziness. The

boundary separating the more hazy from less hazy material was in some

instances rather abrupt and it tended to run more or less parallel to

the machine direction in the film. One sheet of film in which this phenomenon was particularly evident was from roll 311071 of Category IV.

To investigate the possibility that differences in mechanical performance might be associated with differences in haziness a set of twelve

specimens were cut initially from one 8 inch by 8 inch piece from roll

311071 , six from the more hazy region and six from the less hazy region.

All twelve were cut parallel to the transverse direction in the film and

the tensile tests were carried out at -70®C. The results are presented

in Table 18. The initial twelve specimens are identified as MH1 -MH6

(more hazy) and LH1 -LH6 (less hazy). The result was that only one of

the six specimens cut from the more hazy region extended more than 100$,

whereas all six specimens cut from the less hazy region extended more

than 280$.
20

As a result of this observation, seven more specimens were cut from areas surrounding the more hazy region from which the original six were

cut. The latter seven specimens are identified in Table 18 as MH7-MH13-

All seven of these extended at least 388?. The reason why five of the

first six specimens from the more hazy region failed at much smaller

strains remains unknown. All nineteen specimens were handled and tested

under identical conditions. Moreover the first twelve specimens were

tested by alternating between specimens cut from the more hazy and less

hazy material. It is possible that, by chance, the first six specimens

were cut from a small but particularly weak area of the film.

Because of the above observations all the pieces of film from the ten

rolls of the Category III film and at least six rolls from each of the

Category I, II, and IV films supplied by the NSBF were examined visually

for haziness. None of the ten rolls of Category III film were found to

exhibit any significant variation in haziness. On the other hand, all

the film examined from Categories I, II, and IV did contain at least one region which exhibited more hazy and less hazy areas. The one piece of

film from Category B1 which we received did not show any variability in

haziness.

After the above mentioned inspection of the various films, it was decided to examine the mechanical behavior of one of the more hazy regions

observed in the Category II film. Eight specimens were cut along the

transverse direction from roll 313865, gore 53. The results of tensile

tests done at -70°C are shown in Table 19. Although two specimens

failed at a strain of less than 250?, the strains, on average, are not

greatly different from those found earlier for the same roll of film

(see Table 13). Both the average stress at break and average yield

stress are, however, significantly smaller (compare with data in Table

13 and Table 15 respectively).

( vi) Wide Strip Geometry

In addition to the tensile tests just described, we have also examined

briefly the mechanical properties of film specimens having different

geometries or subjected to different deformation modes. The first of

these to be discussed involves the extension of a wide strip of film.

In the work described above the ratio of the specimen width to the , length was 0.52. In the present case the width was set at 1 .87 cm and

the gage length set at 0.2cm, so that the width to gauge length ratio was

9.35. A width of 1 .87cra corresponds to the maximum dimension which can

be accommodated in our present set of grips. Table 20 summarizes the

results of measurements made at 23°C on films from Categories I, II, and

III. All of the specimens were cut so that the transverse film direction was parallel to the tension axis. In each case the average strain

at break is significantly greater, from 18 to 31?. than for the narrower

tensile specimens used earlier (see Table 10). One specimen from the

Category III film elongated by as much as 1030? before failing.
21

(vii) Bubble Inflation

Another technique which can be used to investigate the mechanical performance of biaxially oriented films is one involving the inflation of a diaphragm to form a bubble. This method is described in reference [18]

and is very similar to the ’’race track” test used by the NSBF. An example is shown in Figure 30. The film is inflated from one side to form a bubble. Provided the film is sufficiently thin and the deformations

small the bubble will approximate very closely a spherical shape. Near

the pole the deformation is ' equal -biaxial ' and the true stress in the

region is given by

where P is the inflation pressure, r is the radius of curvature, h is

the initial film thickness, and A is the stretch ratio given by X=1+e, e being the strain determined along a given radius. If the deformation

becomes large enough that the yield point is exceeded, the bubble may

become distorted and no longer spherical in shape. Under a constant inflation pressure creep will occur. If either sufficient time is allowed

or the pressure is high enough, the material will eventually reach a point of instability and necking followed by cold drawing may occur

prior to rupture.

Using this inflation method one sheet of Category III film was gradually

inflated by slowly increasing the pressure until yielding and rupture

occurred. The area of our diaphragm tester was 46cm2 and the test was conducted at 23°C. The example shown in Figure 30 is Category III just

prior to rupture. A characteristic of the film was the formation of nu- merous ”necks” or thinned down regions. In Figure 30 more than 10 different necked down regions were observed over the central region of the

bubble. In each case the necking originated from one or more thin faintly

visible lines which ran nearly parallel to the machine direction in the

film. Upon formation of a neck, cold drawing then occurred with the deformation

being greater in the transverse direction.

(viii) An Example of the Influence of Molecular Weight and Molecular

Weight Distribution on the Tensile Properties of Polyethylene

In Section B of this report it was found that of the five categories of

film the Category III film had a somewhat greater proportion of high molecular weight material than did the others, whereas the Category B-1

film had the lowest molecular weight. It is well known that factors

such as molecular weight and molecular weight distribution play an important role in determining the tensile properties of polymers, particularly semicrystalline polymers such as polyethylene. In this section we shall present one example of how molecular weight and molecular weight

distribution can influence the uniaxial creep behavior of initially

unoriented linear polyethylenes [19] at 23 C.
22

Figures 31 » 32, and 33 present what we shall refer to as isochronal

stress-strain surfaces obtained from creep experiments on three different samples of linear polyethylenes. Although the particular surfaces

shown are for linear polyethylenes in uniaxial creep, a similar set of

surfaces will exist for branched polyethylenes under uniaxial or biaxial

deformations. The surfaces were obtained in the following way. For

each of the three different samples a set of uniaxial creep experiments

was carried out at different levels of applied engineering stress. Each

creep experiment was continued until fracture occurred. In some cases

this meant conducting the experiment for a period of several months.

From each of the sets of creep curves a series of isochrones was determined, as shown in the figures. All three samples were linear

polyethylenes having very nearly the same number average molecular

weight (M^=i 5, 300-1 5,600) , but different weight average molecular

weights (M^=99, 000-1 92,000) . In the present case a greater implies a greater proportion of higher molecular weight components.

The fracture behavior of linear polyethylene in uniaxial creep can be

described by two distinctly different mechanisms. For relatively large

applied stresses the polymer creeps until a material instability occurs

beyond which yielding, cold drawing, and eventually fracture occur. As we shall see presently, the amount of cold drawing which occurs prior to

fracture depends strongly on the molecular weight distribution. At much

smaller applied stresses, or very long failure times, fracture occurs as

a result of crack formation and growth. In this region fracture may occur well before the macroscopic yield point is reached. This region is

not pertinent to the present discussion.

Figure 31 shows a series of isochrones from the sample having the smallest Line a represents for each value of applied stress the time and

strain (plotted as log strain) at which neck formation occurs. Line Y

corresponds to the same two measures at the point of fracture. Since in

this material the specimens all fractured immediately following neck

formation, lines a and Y are the same line.

A similar plot is shown in Figure 32 for the polymer having an of

160,000. In this case it can be seen that, depending upon the level of

applied stress, a significant amount of cold drawing can occur and cor- respondingly a substantially greater lifetime. At the optimum stress,

this material is capable of elongating as much as 25 times before fracture occurs. In Figure 32 the line B represents the strain at which the

neck had propagated the entire gage length of the specimen.

By increasing the to 192,000 the diagram shown in Figure 33 is obtained. Although similar in shape to Figure 32, two distinct differences appear. Firstly the maximum elongation which can be achieved is

somewhat less (18-20^6), and secondly the breadth of the region in stress

in which a significant amount of cold drawing can occur is greater. A

third difference, and one which possibly may be of importance within the

context of film behavior, is the following. At a given stress level the

time to fracture depends upon M^. For example, at a stress of 20MPa the

polymer having an of 1 60,000 fractured in a time of about one to two
23

hours. By increasing the to 192,000 the time to fracture has been

increased to nearly 10 hours. Therefore a small increase in the proportion of higher molecular weight components can lead to a substantially

longer lifetime. The point to be made here is that the principle difference in behavior resulting from the small change in occurs in the

region beyond the yield point. Both materials exhibit yield and necking

at approximately the same strain and time under creep.

I . Summary

The following features of five polyethylene films (Categories I-IY and

B1 ) have been examined: molecular weight, molecular weight distribution^

branching, melting behavior, density (crystallinity), surface texture,

birefringence, crystalline orientation, uniaxial deformation in the

machine (M) and in the transverse (T) directions, and the effect of

sample geometry on deformation behavior. In addition, observations

concerning additive(s) in the films have been obtained, and a preliminary experiment on biaxial deformation of one of the films has

been performed.

Among the features enumerated above clear differences between the films

were observed in their molecular weights-molecular weight distributions.

The intrinsic viscosity was highest (1.27 dl/g) for the Cat. Ill and

Cat. II films, lowest for the B1 film (1.13 dl/g), and was between these

extremes in the case of the Cat. I (1.23) and Cat. IV (1.22) films. The

size exclusion chromatograms of all the films showed evidence of a bimodal distribution with a hint of a third peak. These features are likely to be the result of a blending of polymers. Comparison of the

normalized chromatograms showed that within the calibration limits of

the separation columns used (M.Wts. 850-4.6x10^) the Cat. Ill film

contained a larger proportion of high molecular weight species than the

other films and, on a relative basis, had the highest M^, followed in

decreasing order of molecular weight by the Cat. II, Categories I and

IV, and B1 films.

In so far as branching is concerned, the methyl group content as determined by Fourier Transform Infrared Spectroscopy was found to be

the same for all the films, i.e. ^^2.1 methyl groups/100 carbon atoms.

The fact that the DSC (Differential Scanning Calorimetry) curves of all

the films exhibited a polymer melting endotherm whose peak was in the

narrow temperature range 1 05.5 °C-1 07°C, and that the crystallinities of

the films (based on density measurements) were found to be close to one another (46. 256-48. 2^) , are consistent with the methyl group content

being the same for the various films. The DSC experiments revealed the

presence in all the films of a small quantity of a component which melts

at a much lower temperature than the bulk of the polymer. This low

melting component is most probably additive material . The presence of

additive was also indicated in FTIR spectra which exhibited extra

absorption bands which are not known bands of polyethylene. The extra

bands were however different for the B1 film than for the Cat. I-IV

films.
2H

The crystalline orientation in the films was probed by taking wide angle

x-ray diffraction patterns with the x-ray beam parallel to the T, M and

N (normal to the film) directions. The results indicate that there are qualitative similarities between the preferred orientations of the

microcrystalline regions in the various films. The indications are (1)

that the a-axis tends to be oriented preferentially parallel to the MT

plane and preferentially parallel to M in that plane, and that (2) the

b-axis tends to be preferentially oriented parallel to the NT plane and

preferentially parallel to N in that plane. Infrared spectroscopic data

were obtained which are consistent with these observations. An idealized working model is suggested in which it is envisaged that crystalline regions in the films consist mainly of two populations of

microcrystals having different preferred orientations (Fig. 25) relative

to T, M and N. This model must remain speculative pending ' quantitative

studies and comparisons of the orientation(s ) and orientation distributions in the films using an automated counter-diffractometer system

equipped with a four circle goniometer sample holder.

When viewed along the N direction the Category I, II, IV and B1 films,

as well as virgin Cat. Ill film, exhibited negative birefringence with

respect to M, i.e. n(M)<n(T) . The magnitudes of the birefringences

measured for all the films were collectively very small (in the

range-[ 0.0009 to 0.0019 ] and, correspondingly, any differences between

the films were also small. This latter observation is consistent with

the similarity in the character of the crystalline orientations in the

various films suggested by the WAXD and Infrared Spectroscopic

examinations of the films, provided it is assumed that the contribution

of the disordered regions to the total birefringence in the MT plane is

the same for all the films.

In the area of mechanical properties it was established that in uniaxial

constant rate of strain experiments the extension to break is dependent

on specimen geometry, i.e. on the sample length/breadth ratio. Decreasing the length/breadth ratio results in an increase in the extension to

break at 23°C. A length/breadth ratio of 1.9 was used in the experiments which were carried out at 23 °C and -70 °C using a strain rate of

991^/min. A summary of the tensile data in Tables 9-15 is given in table 21 .

Concerning the NSBF criterion that the strain to break should not be

less than 250^5 in either the M or T directions at -70°C, it was found

that although the average strain to break of each of the five films

met that requirement, the Category III film was the only one for which

none of the measurements fell below 250 %.

The Cat. II, III and IV films exhibited higher average extensions to

break parallel to T than to M at both 23°C and -70°C. In contrast, the

average strains to break in both directions for the Cat. I film were essentially the same at 23 °C, furthermore at -70 °C the extension to
25

break was higher in the M direction. The extension to break behavior of

the B1 film in the M relative to the T direction was similar to that of

the Cat. I at 23 °C and to that of the Cat. II, III and IV at -70 °C.

The overall haziness exhibited by all the films is due, in part at any

rate, to the roughness of both their surfaces at which variations in topography occur on a lateral scale of a few pm. Differences in haziness

to the naked eye (under appropriate illumination) were observed in

adjoining regions in some portions of the Cat I, II and IV films. The

boundary between the hazy and less hazy regions was usually roughly parallel to M. A brief examination of whether there are differences in

birefringence and/or mechanical behavior between adjoining hazy and less

hazy regions was carried out. In view of the scatter in the relatively

few measurements which were made, some of the results which might be

interpreted as evidencing differences in birefringence and/or mechanical

properties between the differently hazy regions in the films must remain

tentative at this juncture. The scatter in the measurements is not

unlike the scatter experienced in similar measurements made in regions

of apparently uniform haziness.

J. Concluding Remarks

This exploratory study has resulted in the identification of

similarities and differences between various features of the films.

Close similarities have been found in methyl group content,

crystallinity, and peak melting temperature. The preferred orientations

in the crystalline regions (i.e. relative to the M, T, and N directions)

appear to be qualitatively similar. However, due to the limited scope

of the orientation studies, the question of whether there are differences in the orientation distributions of the microcrystals

between the films remains open pending the determination and comparison

of the pole figures of each film.

Differences between the films have been revealed in two features, namely

between their molecular weights, and in the balance of the strain to

break behavior in the M relative to the T directions. These two types

of differences are particularly evident between the Cat. Ill, Cat. I' and

B1 films.

Differences in response to tensile deformation in the M relative to the

T directions point to underlying built-in differences in fine structural

anisotropies in the films with respect to these directions. One or both

of two possibilities suggest themselves in this connection: (1)

Differences in the distribution of the orientations of the

microcrystalline regions, hence the need for quantitative comparisons of

the crystalline orientation characteristics of the films: (2)

differences in the nature of and degree of any chain orientation in the

disordered regions which are interspersed between the constituent

microcrystals in the films. Differences of the latter type [i.e. type

(2)] are difficult to determine. In any event determination of the

crystalline orientation characteristics of the films would be a necessary first step in this latter connection. Added to these various
26

considerations are the differences in molecular weight between the

films, the effects of which remain unclear at this stage. The influence

which differences in molecular weight can have on the mechanical behavior of initially unoriented polyethylene was illustrated in the example

discussed in Section H(viii). However, in the case of the films investigated in this study, determination of any effects of molecular weight

per se on the mechanical properties of the films is complicated by the

fact that the films are not isotropic.

In addition to the determination of the pole figures of the films, it is

recommended that future studies include: (a) An examination of

the biaxial (bubble geometry) deformation characteristics of the films

at 23 °C and -70 °C. Biaxial deformation experiments address themselves

more directly than uniaxial ones to the question of the importance of

the type of imbalance which exists between the mechanical properties in

the M and T directions, (b) As background to developing an understanding of the possible intrinsic influence of differences in

molecular weight between the films on their mechanical properties, creep

to failure experiments of the type described in Section H(viii) should

be carried out on unoriented sheets of polymer from each film. Such

sheets can be prepared by melting and subsequently cooling several

compacted layers of film.
27

K . References

1. Drott, E.E., and Mendelson, R. A., J. Polymer Sci., Part A-2, _8, 559

(1 973).

2. Wagner, H. L. and McCrackin, F. L. , J. Appl. Polymer Sci., 21 , 2833

(1977).

3. Zimm, B. H. , and Stockmayer, W. H. , J. Chem. Phys. 1

, 1301 (1949).

4. Rueda, D. R., Balta’-Calleja, F. J., and Hildalgo, A.,

Spectrochemica Acta 35A, 847 (1979).

5. Bunn, C. W., Trans. Faraday Soc. 39_, 482 (1939).

6. Davis, G. T. , Eby, R. K., J. Appl. Phys. 4274 (1973).

7. Stehling, F. C., Speed, C. S., and Westerman, L., Macromolecules,

U_, 698 (1981 )

8. Tabar , R. J., Murray, C. T. , and Stein, R. S., J. Polymer Sci.

Polym. Phys. Ed. 83T (1984).

9. Stein, R. S., and Wilkes, G. L., in Structure and Properties of

Oriented Polymers (I.M. Ward edit.) Chapt. 3» Wiley N.Y. (1975).

10. Mead, W. T., Desper, C. R. and Porter, R. S., J. Polymer Sci.,

Polymer Phys. Ed. 17, 859 (1979).

- . .

11. Bunn, C. W., and Daubeny, R. De P.,

(1954).

• Trans

Faraday Soc50 . 1173

12. Lindemeyer, P. H.

,

(1 965).

and Lustig, S. , J . Appl . Polymer Sci ., i, 227

13. Maddams, W. F. and

(1978).

Preedy, J. E. , J. Appl

Polymer Sci

22, 2721

14. Maddams, W. F. and

(1 978).

Preedy, J. E., J. ApplPolymer Sci

22, 2739

15. Maddams, W. F. and

(1 978).

PReddy, J. E., J. Appl

Polymer Sci

22, 2751

16. Alexander, L. E., X-Ray Diffraction Methods in Polymer Science,

Wiley, N.Y. (1969).

17. Krimm, S. 'Infrared Spectra of Solids: Dichroism and Polymers’, in

Infrared Spectroscopy and Molecular Structure (Ed. M. Davies)

Elsevier, Amsterdam (1963).
28

18. Webb, L. D., Engineering Services Final Report, prepared for NSBF,

National Center for Atmospheric Research, Palestine, Texas.

Contract #NCAR1-73, Project #TAMRF-921

19. Zapas, L. J. , and Crissman, J. M., ACS Symposium Series #95,

Durability Of Macromolecular Materials (R. K. Eby Ed.) 301 (1978).
29

List of Tables

1. Limiting Viscosity Number of Polyethylenes

2. 'Apparent' Molecular Weights (SEC)

3. Comparison of Methyl Group Content of Polyethylene Films from the

Analysis of the Infrared Spectral Region 1 328-1 400cm“^

4. Density of Polyethylene Films at 23.0±0.1°C

5. Differential Scanning Calorimetry of Films

6 . Birefringence of Films

7. Birefringence on Either Side of Boundary between Hazy and Less Hazy

Regions

8 . Intensity Ratios of -CH2 Rocking Bands

9. Summary of Ultimate Properties for the Category I and II Films at

230

10. Tensile Properties of Ballon Films at 23°C.

11. Maximum and Minimum Values of Strain at Break at 23 °C

12. Summary of Yield Stress Data Obtained from Tensile Tests at 23°C

13 . Tensile Properties of Balloon Film at -70°C

14. Maximum and Minimum Values of Strain at Break at -70°C

15 . Summary of Yield Stress Data obtained from Tensile Tests at ~70°C

16. Summary of Tensile Properties of Balloon Film as a Function of

Strain Rate at -70 °C

17 . Summary of Tensile Properties of Category I Film

18 . Summary of Tensile Properties of Specimens Cut from both Hazy

and less Hazy Category IV Film at -70°C. (Transverse Direction

Only).

19. Summary of Tensile Properties at -70°C for Specimens Cut From One

Hazy Region of Category II Film. (Transverse Direction Only).

20. Ultimate Properties at 23°C for Specimens 1.87cm wide and a Gage

Length of 0.20 cm. (Transverse Direction Only).

21. Summary of Tensile Properties at 23°C and -70°C (from Tables

10-15)
30

List of Figures

Fig. 1. Normalized Size Exclusion Chromatographs of the Category I and

Category II films (Table 2, Series A).

Fig. 2. Normalized Size Exclusion Chromatographs of the Category I and

Category III films (Table 2, Series A).

Fig. 3. Normalized Size Exclusion Chromatographs of the Category I and

Category IV films (Table 2, Series A).

Fig. 4. Normalized Size Exclusion Chromatographs of the B1 film, and the raw polymer pellets from which it was produced (Table 2,

Series B).

Fig. 5. Normalized Size Exclusion Chromatographs of the B1 and Category

I films (Table 2, Series B).

Fig. 6. Normalized Size Exclusion Chromatographs of the B1 and Category

III film (Table 2, Series B)

Fig. 7. Room temperature Infrared Spectra in the frequency range

1 328cm~^ -l400cm“^ , obtained from the five categories of film

after they had been melted and then cooled to room temperature

(see text).

Fig. 8. Difference Spectrum B1 - Category I.

Fig. 9a. DSC heating curve

,

Category I film.

Fig. 9b. DSC heating curve

,

Category I film (expanded vertical scale).

Fig. 9c. DSC cooling curve

,

Category I film.

Fig. 9d. DSC cooling curve

,

Category I (expanded vertical scale) •

Fig. 10a. DSC heating curve

,

Category II film.

Fig. 10b. DSC heating curve

,

Category II film (expanded vertical scale )

Fig. 10c. DSC cooling curve

,

Category II film.

Fig. lOd. DSC cooling curve

,

Category II film (expanded vertical scale )

Fig. 11a. DSC heating curve

,

Category III film.

Fig. 11b. DSC heating curve

,

Category Ill film (expanded vertical scale )

Fig. 11c. DSC cooling curve

,

Category III film.

Fig. lid. DSC cooling curve

,

Category Ill film (expanded vertical scale )

Fig. 12a. DSC heating curve

,

Category IV film.
31

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

12b. DSC heating curve

,

Category IV film (expanded vertical scale )

12c. DSC cooling curve

,

Category IV film.

12d. DSC cooling curve

,

Category IV film (expanded vertical scale )

1 3a . DSC heating curve

,

B1 film.

13b. DSC cooling curve

,

B1 film.

14. Phase Contrast Micrographs of Category I film (#315477).

(a) Actual film, (b) and (c) are replicas of areas on opposite

surfaces

15. Phase Contrast Micrographs of Category II film (7#31 3865-53 ) • (a) Actual film, (b) and (c) are replicas of areas on opposite

surfaces

16. Phase Contrast Micrographs of Category III film (#112858-177).

(a) Actual film, (b) and (c) are replicas of areas on opposite

surfaces

17. Phase Contrast Micrographs of Category IV film (#311071).

(a) Actual film, (b) and (c) are replicas of areas on opposite

surfaces

18. Phase Contrast Micrographs of Category B1 film (#367006).

(a) Actual film, (b) and (c) are replicas of areas on opposite

surfaces. Particles marked X are discussed in the text.

19. Scanning Electro Micrograph of one of the surfaces of Category I (#315420) film.

20. Wide angle x-ray diffraction patterns of Category I film

(#31 5420). (a) x-ray beam parallel to T, (b) x-ray beam

parallel to M, (c) x-ray beam parallel to N.

21 . Wide angle x-ray diffraction patterns of Category II film

(#313865, Gore 53). (a) x-ray beam parallel to T, (b) x-ray

beam parallel to M, (c) x-ray beam parallel to N.

22. Wide angle x-ray diffraction patterns of Category III film

(#112877). (a) x-ray beam parallel to T, (b) x-ray beam

parallel to M, (c) x-ray beam parallel to N.

23. Wide angle x-ray diffraction patterns of Category IV film

(#311071). (a) x-ray beam parallel to T, (b) x-ray beam

parallel to M, (c) x-ray beam parallel to N.

24. Wide angle x-ray diffraction patterns of B1 film (#367006).

(a) x-ray beam parallel to T, (b) x-ray beam parallel to M,

(c) x-ray beam parallel to N.
32

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

Fig.

25. Schematic representation of two idealized microcrystal

orientations in a film, (a) The microcrystals are oriented with

the b-axis parallel to N, and the a-axis (and hence the c-axis

also) oriented randomly in the MT plane, (b) the microcrystals

are oriented with the a-axis parallel to M, and the b-axis (and

c-axis) oriented randomly in the NT plane (see text).

26. Polarized Infrared Spectra of films in the region 675cm“1-775cm“^

Dotted lines and full lines correspond to the plane of

polarization parallel and perpendicular to M respectively.

(a) Category I, (b) Category II, (c) Category III, (d) Category

IV, (e) B1 .

27. Creep strain {%) versus time for specimens of balloon film at

23°C and an applied stress of 2.5 MPa (364 psi). Solid symbols

- transverse direction, open symbols - machine direction;

squares - Category I, inverted triangles - Category II, circles

- Category III, triangles - Category IV.

28. Creep strain {%) versus time for specimens of balloon film at

23°C and an applied stress of 10 MPa (1450 psi). Solid symbols

- transverse direction, open symbols - machine direction;

squares - Category I, inverted triangles - Category II, circles

- Category III, triangles - Category IV.

29. % strain at break versus yield stress for 64 specimens of

balloon film at -70°C. Strain rate 991^ per minute; circles - Category I, inverted triangles - Category II, squares - Category

III, triangles - Category IV, crosses - Category B1

30. An example of biaxially oriented film under inflation.

31 . Failure envelope at 23°C for linear polyethylene with M^ = 15,300 and M^ = 99,000. Log percent elongation versus engineering stress for various isochrones obtained from uniaxial

creep data. Line a corresponds to necking and line T to

fracture

32. Failure envelope at 23°C for linear polyethylene with M^ = 15,000 and M^ = 160,000. Log percent elongation versus engineering stress for various isochrones obtained from uniaxial

creep data. Line a corresponds to necking line 8 to the fully

necked condition, and Y to fracture.

33. Failure envelope at 23°C for linear polyethylene with M^ = 15,600 and M^ = 192,000. Symbols have the same meaning as in

Fig. 24.
33

Category

I (Set 13)

II (Set 15)

III (W^I.47-3)

IV (6/3/82)

B1 - film

B1 - pellets

Table 1

LIMITING VISCOSITY NUMBER OF POLYETHYLENES

(TRICHLOROBENZENE AT 130 C)

Roll # (Gore)

315420

313865 (53)

112858 (177)

31 1071

367006 Series 03

Limiting Viscosity Number (

1 .23

1 .27

1 .27

1.22

1.13

1.13

) dl/g
m

im\ fWM%

,MS

VTWfc'^Ky ;,v

iff

y-’fls''.' i

iW” M'WaIv'W

'T^t‘>^'i0r~

W--

ia

:y ftenn’-.; snn#.

'-,5\ i9^¥7.m^iv}

[T«f»

<4./* '/'' « *1*^!

' .."'I'm' ’€

i>«^.' -„L i .jMi-S'&’

' t Iffi' '•' *

. J

pi'jiii

^.v

ti

iM'W'^ m r-:>vt m

WnV:! Wife miM

tJi
34

Table 2

Category

'APPARENT' MOLECULAR WEIGHTS (SEC)

Roll (Gore) 'Apparent' Molecular Wt.*

Mw Mn

I (Set 13) 315420 216000

202000

22300

23100

(Series

(Series

A)

B)

II (Set 15) 313865(53) 243000 23200 (Series A)

III (W41.47-3) 112858(177) 253000 29000 (Series A)

• 255000 30100 (Series B)

IV (6/3/82) 311071 209000 21700 (Series A)

B1 film 367006 154600 22400 (Series B)

B1 pellets - 147800 21500 (Series B)

*The 'apparent* Mn and Mw values given in this table were derived from the

analysis of the size exclusion chromatograms (Figs. 1-6) using the

assumption that the polyethylene chains are linear. Actual Mn and Mw

values are likely to be higher than those listed here due to the effects

of branching and because material with molecular weight greater than

-4.5X10^ is beyond the range of the separation capabilities of the SEC

columns used. Both these limitations are discussed in Section B(ii) of

the report.
»

Wili-.'IW , r',^

^

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^ i

e^QgfS

^^^Boi4?»ex:'^ oorog

" ^ouss

asiy^Z) POSTS

llB

Ma.«

,. '• -'V.0 ^

" / -i*M^ t^U^laa . -^' (Et ^•^.1:

'9

'J'

, -.S',

(nri«?Bsn tg-T<»,ftJM)-IIIii

rorre

op^sr 'S >ooT»c *T“

fS0\es.d)^

: ^fjr''

.- - r|(| jXigB.-

4*C B^^xia<i.f0

;(ofrr*"

noi*i/IfW» •pit imU «l8^ifiii|^)

'^ijwto «ii#l‘t<*^®tXoa «^«W no^lIqaB/ee^:'^

©K?' ^jto'yj^^^bttwx^b i?t»w ^vil^ 9%{^iM^ wH Jiot nM

eif# <t** f noi*i/I(
35

Table 3

COMPARISON OF METHYL GROUP CONTENT OF POLYETHYLENT: FILMS

FROM THE ANALYSIS OF THE INFRARED SPECTRAL REGION 1 328-1 ^400 CM“^

Resolved Methyl

Total Integrated Band Peak Intensity

Area 1 328-1 ilOOcm"'' at 1378cn"''

Category Roll i (Gore) (A)cm“^ (P) Ratio P

I (Set 13) 315^120 5.376 0.15 0.0279

II (Set 15) 313865(53) 6.01 0.165 • 0.0275

III (Win.i17-3) 112858(177) 5.65 0.155^ 0.C275

IV (6/3/82) 31 1071 6.11 0.171 0.0230

B1 (Film) 376006 6.38 0.184 0.0238

36

Table 4

DENSITY OF POLYETHYLENE FILMS AT 23-0 ± O.T’C

Category Roll # (Gore)

I (Set 13) 315420

II (Set 15) 313865(53)

III (W41.47-3) 112858(177)

IV (6/3/82) 311071

B1 367006

^Error less than ±0.0005 g/cc.

Weight %

Density (g/cc)'*' Crystallinity (X)

0.9165 46.4

0.9170 46.8

0.9175 47.1

0.9185 47.8

0.9163 46.2

0.9170 46.8

0.9165 46.4

0.9170 46.8

0.9190 48.2

0.9190 48.2

37

Film Category

I (Set 13)

II (Set 15)

III (Win.H7-3)

IV (6/3/32)

B1

Table 5

DIFFERENTIAL SCANNING CALORIMETRY OF FILMS

Roll if (Gore)

* Main Melting** Main Crystn* Low Temp

*» Low Temp.

Peak , °C Peak, ®C Melting ?eak,°C Crystn Peak

315420 106.8 94.4 54.4 58.3

3113365(53) 107.1 94.1 51 .6 58.4

122858(177) 106.2 93.0 51 .8 57.2

311071 106.6 93.3 51 .5 56.7

367006 105.5 91.1 47.8 53.6

^^Heating cycle: Rate of heating 20°C/min.

»*Cooling Cycle: Rate of cooling -20°C/min.
^1
38

Table 6

BIREFRINGENCE OF FILMS An

Average* An

(Film Thickness) Roll # (Gore) (range)

I (0.7 mil) 315420 -0.0018

(-0.0016 to 0.0019)

II (0.8 mil) 313865(53) -0.0015

(-0.0013 to -0.0018)

IV (6/3/82) (0.8 mil) 311071 -0.0013

(-0.0012 to -0.0015)

B1 (0.8 mil)

- 367006 -0.0017

(-0.0015 to -0.0019)

III (0.8 mil) 112858(177) n (M) > (T)

See text

III (0.8 mil) 112877 -0.0011

(-0.0009 to -0.0012)

*Average of nine measurements

An = n(M) - n(T) = Y/t is the birefringence in the MT plane.

Y = retardation

t = nominal thickness of film (I, 0.7 mil = 17780 nm; II, III, IV,

B1 , 0.8 mil = 20320 nm)

Precision in measuring Y « ± 1 nm which for films 0.7-0. 8 mil thick

corresponds to a difference in birefringence of less than ± 0.0001
iaaaLi&JIsS

i-

‘‘ <|r0f(-,05.;.#fe^^^^^

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dOOTS?.

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-ffi ," ,," vsiS^’' '''vf

BSI. " lyi-^ (s8\E\d):;y;

- . . "3 ' -V«»r B

' (XiJi^8iO)^il

<Xis 8.tt)f IE

f^Si f Ui«’b,o)“ii:

.,,, —— , i^nlfl la( 9|BnaY4'

; a/ii; aX 4'Kt *' ^

1X9 B,ty . 5tioXrt^^,’p» uc; f i • f ni,

6 4 t^-3' sEii?95nXi5dTi<< nt s WX R-iaoqrft'ioji'
39

Table 7

BIREFRINGENCE An ON EITHER SIDE OF BOUNDARY

BETWEEN HAZY AND LESS HAZY REGIONS

Cat I Cat II Cat IV

#315420 #313865 (53) #31 1071

An An (e An

-0.0018 (19. 5<’) -0.001

-0.0013 -0.0012 (19.4°) -0.001

-0.0013 -0.0016 (19.1°) -0.001

Less Hazy -0.001

-0.0015 (18°) -0.0015

Av. =-0.0012 Av=-0.0015 Av=-0.0014

Hazy -0.0015 -0.001

(20°) -0.001

-0.0015 -0.0013 (17.2°) -0.0013

-0.0017 -0.0009 (16.5°) -0.0013

-0.0010 (15.5°) -0.0013

Av=-0.0016 Av=-0.0011 Av=-0.0013

*The boundary between the less hazy and the hazy regions runs closely

parallel to the machine direction. The birefringence measurements in the

two regions were made at 3 mm increments away from the boundary.

**In the case of Category II, extinction between crossed polarizer and

analyzer in the hazy and less hazy regions occurred when the machine

direction deviated from the plane of polarization of the polarizer by an angle 9 (15.5°=20°) appreciably larger than uncertainties associated in

identifying the machine direction exactly. The birefringence in this

column represents the difference in refractive index for light polarized

parallel and perpendicular to the extinction direction.
rfoOiO^

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0- ' ’ troo.c^

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t3si’1k^6^?;‘4flgi^^’«*tp^ 9T(J itar*»*Ki»'f/;_nawj[oi). J
40

Table 8

INTENSITY RATIOS OF -CH2 ROCKING BANDS

Category

* Parallel/Perpendicular

733 cm"''

* Perpendicular/Parallel

719 cm"''

I #315420 1 .37 1 .38

II #313865(53) 1.49 1 .51

III #112858(177) 1.17 1 .24

IV #311071 1 .60 1 .72

B1 #367006 1 .26 1 .25

^Parallel and perpendicular refer to polarization parallel and

perpendicular to the machine direction M or to the extinction direction

closest to M.

41

Table 9

SUMMARY OF ULTIMATE PROPERTIES FOR THE

CATEGORY I AND II 'FILMS AT 23°C

Category

Stretching

Direction^^^

Average

Strain at break^^) ^^)

(%) €

Standard

Deviation

{%)

Tensile Stress

at Break

(MPa)

Standard

Deviation

(MPa)

1(d) M 286 31 19.2(2800 PSD 1 .0 Kd) T 339 28 21 .5(3120 PSD 1 .9 iKe) M 250 17 18.0(2610 PSD 1 .8 Il(e) T 410 35 18.9(2740 PSD 1 .2

(a) M - Machine Direction, T - Transverse Direction

(b) e = 100

(c) average for six specimens

(d) Category I (Set 13), Roll #315^20

(e) Category II (Set 15), Roll #313865 (Gore 53)

42

Table 10

TENSILE PROPERTIES OF BALLOON FILM AT 23 °C

Category

Roll

Number

Gore

Number

Cutting

Direction^^)

Average

Strain at

Break^^''^)

(%) e

Average

Standard Stress

Deviation at Break

{%) (MPa)(^)

Standard

Deviation

(MPa)

I 315^77 M Jl62 33 25.4 1 .3

I 315^177 - 1 H5l1 19 29.0 1 .6

II 313865 53 M 1182 39 22.5 0.7

II 313865 53 T 559 27 25.6 1 .4

III 111958 121 M ilil5 50 26.7 1.4

III 111958 121 T 624 27 26.5 1 .3

IV 311071 - M 483 88 22.2 3.0

IV 311071 - T 577 75 23.5 2.4

B1 367006 - M 491 40 27.7 1 .8

B1 3167006 T 470 33 34.0 2.8

Strain Rate 991%/min.

(a) M

- machine direction, T - transverse direction

(b) Averages are for 6 specimens, gage length = 0.60 cm, width = 0.315 cm.

(c) E = 100

(d) 1 MPa = I'i5.03 psi.
'^'^Sl'^" ,nVli*i>^ 't^^5y8£i>0 ' ^

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^ 3

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,^\{^t-X) (» 0 r - a («)‘j

eo.|t^? • <bM
43

Table 11

MAXIMUM AND MINIMUM VALUES OF STRAIN AT BREAK AT 23 °c

Roll Gore Cutting £ (Max) e(Min)

Category Number Number Direction i%) (%)

I 315477 M 498 408

I 315477 - T 477 428

II 313865 53 M 516 418

II 313865 53 T 593 521

III 111958 121 M 500 371

III 111958 121 T 655 588

IV 311071 - M 568 325

IV 31 1071 — T 671 495

B1 367006 - M 565 457

B1 367006 - T 508 415

44

Table 12

SUMMARY OF YIELD STRESS DATA OBTAINED FROM TENSILE TESTS AT 23

Average Maximum Minimum

Yield (a) Standard Yield Yield

Film Cutting Stress Deviation Stress Stress

Category Direction (MPa) (MPa) (MPa) (MPa)

I >l(b ) 11.5 0.3 1 2.0 1 1 .2

I 7(b) 10.7 0.5 11.3 10.2

II M 10.8 0.3 11.1 10.6

II T 10.4 0.1 10.5 10.4

III M 11.3 0.4 11.9 1 1 .1 III T 10.3 0.4 11.1 10.0

IV M 10.7 0.3 11.1 10.3

IV T 10.7 0.6 11.1 10.0

B1 M 10.6 0.4 11.1 10.1

B1 T 10.7 0.2 11.1 10.6

(a) Averages are for six specimens.

(b) M-machine direction, T-transverse direction.

45

Table 13

TENSILE PROPERTIES OF BALLOON FILM AT ~70 °C

Category

Roll

Number

Gore

Number

Cutting

Direction^^^

Average

Strain at Break^^^

(?) £

Standard

Deviation

(?)

Average

Stress

at Break

(MPa)

Standard

Deviation

(MPa)

I 315477 _ M 319 (d) 59 60.0 3.4

I 315477 - T 259 (e) 75 56.0 5.3

II 313865 53 M 295 (e) 144 48.4 3.4

II 313865 53 T 3^6 (e) 143 48.7 6.4

III 112861 173 M 327 (d) 44 54.5 4.2

III 11 2861 173 T 434 (e) 135 54.7 3.4

IV 311071 - M 350 (d) 117 47.4 5.1 IV 31 1071 - T 428 (e) 29 53.9 2.1

B1 367006 - M 263 (d) 107 52.0 3.6

B1 367006 - T 382 (d) 67 64.0 5.0

Strain rate 991^/min.

(a) M - machine direction, T - transverse direction.

(b) E = 100 gage length = 0.60 cm, width = 0.315 cm.

(c) 1 MPa - 145.03 psi.

(d) Average for 6 specimens.

(e) Average for 8 specimens.
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46

Table 14

MAXIMUM AND MINIMUM VALUES OF STRAIN AT BREAK AT -70 °C

Strain at Strain at

Roll Gore Cutting Break (max) Break (min)

Category Number Number Direction (%) e (%) e

I 315477 - M 41 3 248

I 315477 - T 377 110

II 313865 53 M 449 46

II 313865 53 T 462 72

III 112861 173 M 369 255

III 112861 173 T 609 258

IV 311071 - M 488 165

IV 311071 - T 480 217

B1 367006 - M 426 114

B1 367006 - T 470 304

47

Table 15

SUMMARY OF YIELD STRESS DATA OBTAINED FROM TENSILE TESTS AT -70 °C

Film

Category

Cutting

Direction

Average

Yield

Stress^^^

(MPa)

Standard

Deviation

(MPa)

Maximum

Yield

Stress

(MPa)

Minimum

Yield

Stress

(MPa)

(a)

(b)

I

) 57.8 4.0 61 .3 51 .8

I 'p(b

)

51 .8 2.4 54.9 49.5

II M 42.9 3.0 48.9 39.4

II T 42.2 3.4 48.3 38.4

III M 46.4 2.5 49.5 42.2

III T 45.7 4.7 54.6 38.7

IV M 42.9 2.9 46.4 37.8

IV T 47.3 4.2 50.5 39.1

B1 M 45.4 3.6 49.5 40.3

B1 T 47.9 3.6 51 .8 42.9

Averages are for six or more specimens.

M-machine direction, T-transverse direction.
yV-Nt

S»- *^^'y‘f"^''***f^ j jj-y »-'*»- «yi fug -"

^ t'f>ea<»T4je M i

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48

Table 1

SUMMARY OF TENSILE PROPERTIES OF BALLOON FILM

AS A FUNCTION OF STRAIN RATE AT -70 °C

Film CategoryRoll # (Gore)

Rate of

Strain

(J/min.

)

Cutting

Direction

Average

Strain

at Break

{%) £

Average

Stress

at Break

(MPa)

1,3154177 9910 M 372 41.4

9910 T 260 44.3

991 M 319 60.0

991 T 259 56.0

99.1 M 301 39.9

99.1 T 296 48.1

11.313915 (22) 9910 M 358 42.3

9910 T 490 58.4

991 M 295 48.4

991 T 346 48.7

99.1 M 297 48.5

99.1 T 332 42.3

B1 ,367006 9910 M 363 52.9

9910 T 328 55.3

991 M 263 52.0

991 T 382 64.0

99.1 M 303 54.6

99.1 T 263 56.5

Averages are for three specimens with the exception of the specimens

tested at a strain rate of 991 %/min for which the averages are for six

specimens
.« 'm

csm-'.r nxisernt^^

omx-r^ '4::^ '"'

"s

m

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49

Table 17

SUMMARY OF TENSILE PROPERTIES

OF CAT. I., FILM

Roll

Number

Area

Temperature

(°C)

Cutting

Direction

Average

Strain

at

Break($ )

Average

Stress

at

Break

(MPa)

Average:

Yield

Stress

(MPa)

315477 23 M 462 25.4 11.5

315477 23 T 454 29.0 10.7

315421 (107) 23 M 498 21 .0 9.3

315421 (107) 23 T 546 23.1 8.9

315421 (111) 23 M 631 26.5 10.4

315421 (1 1 1 ) 23 T 568 27.5 10.6

315477 -70 M 319 60.0 57.8

315477 -70 T 259 56.0 51 .8

315421 (107) -70 M 341 48.5 35.0

315421 (107) -70 T 375 51 .5 42.1

315421 (1 1 1 ) -70 M 446 65.1 50.8

315421 (111

)

-70 T 453 66.6 48.9

(a) Averages are for 3 specimens except for Roll 31 5477 from which 6

specimens were tested . Strain Rate = 991? per minute

-
. A TV?

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50

Table 18

SUMMARY OF TENSILE PROPERTIES OF SPECIMENS CUT

FROM BOTH HAZY AND LESS HAZY CATEGORY IV FILM*

TRANSVERSE DIRECTION ONLY

-70°C

Strain

at Stress at Yield

Specimen Break Break Stress

Number (56)e (MPa) (MPa)

MH1 8 54.4 54.4

MH2 99 46.5 49.4

MH3 74 44.5 52.4

MH4 495 53.4 46.4

MH5 37 34.6 39.5

MH6 74 36.6 35.6

MH7 392 43.5 42.5

MH8 445 41 .5 39.5

MH9 549 47.4 35.6

MH10 487 46.5 43.5

MH1

437 44.5 40.5

MH12 388 42.5 41.5

MH13 598 57.3 42.5

LH1 417 53.4 52.4

LH2 524 51 .9 51 .9

LH3 412 55.4 55.4

LH4 565 48.4 39.5

LH5 594 49.4 36.6

LH6 281 43.5 32.6

Hazy Clear

Average Strain at Break (%) 31 4 466

Average Stress at Break (MPa) 45.6 50.3

Average Yield Stress (MPa) 43.3 44.7

(a) MH = More Hazy , LH = Less Hazy

*Roll 311071
V

m'i' - W S'i^.tn^ wW

^;=a=

3li»4»l?

: & ':

9

- .«

4T

i9

’^•'.14 ?;%: ..1, )/,

;,i(

^imm ^

a-H

TT|l

4‘r^ ^‘-7

'

§ 4<- tfnJ./'-., ,

.;•• V. -;.

' .'• >' •»

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- •

' J * ;KJ *x*»M •tOI • i!M

'i^ rTOfJC'xio^ai
51

Table 19

SUMMARY OF TENSILE PROPERTIES FOR SPECIMENS

CUT FROM ONE HAZY REGION OF THE CATEGORY II FILM*

TRANSVERSE DIRECTION ONLY

-70°C

Strain

Specimen

Number

at

Break

(?)e

Stress at

Break

(MPa)

Yield

Stress

(MPa)

1 280 31 .6 29.6

2 66 31 .6 27.7

3 540 41 .5 29.7

561 40.5 24.7

5 487 39.5 27.7

6 507 42.5 30.6

7 429 31 .6 27.2

8 248 30.6 27.7

Average strain at break = 390?

Average stress at break = 36.2 MPa

Average yield stress = 28.0 MPa

*Roll 313865, Gore 53

52

Table 20

ULTIMATE PROPERTIES AT 23®C FOR SPECIMENS

1.87 CM WIDE AND A GAGE LENGTH OF 0.20 CM

TRANSVERSE DIRECTION ONLY

Film Category

&

Roll Number

Average*

Strain at

Break (%)

Standard

Deviation

%

Average

Stress

at Break

(MPa)

I - 135477 595 96 21 .0

II - 313865 717 94 17.5

gore 53

III - 112861 736 213 17.9

I - 315421 640 19.9

area 106

Standard

Deviation

(MPa)

1 .34

1 .08

1 .65

^averages for six specimens

SUMMARY

OF

TENSILE

PROPERTIES

AT

23°C

AND

-70°C

(FROM

TABLES

10-15)

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LU 2

T

(Sliun 9A|»B| 9a)

}unouiv

Fig.

6.

Normalized

Size

Exclusion

Chromatographs

of

the

B1

and

Category

TIT

films.

(Table

2,

Series

B)

fteSORB.^NCL

60

Fig. 7. Room temperature Infrared Spectra in the frequency range

1328 cm ^ - 1400 cm“l, obtained from the five categories

of film after they had been melted and then cooled to

room temperature (see text)
imi> moS

"*o eJEx

Um p^pii mLi^ io

liat'1 j*at) , diimw-^iOBj aoon
flBSaRBANCE

.00

.1

61

a

(\j

Fig. 8. Difference Spectrum B1 - Category I,

3.03

62

<00N3 3S/1V3W

TEMPERATURE

(C)

0STJ

63

a

<u53O

tocaa

x:o

c/3 QX

as

CO

TH

Oi

TEMPERATURE

CQ

DSC

3.(]0

64

ca <0QN3 33S/1V3W

TEMPERATURE

CC)

DSC

NORMALIZED

Cl

CSET

13)

R^y31b420

SCAN:

1C

WT»

1.

08

mg

SCAN

RATE:

-20.00

dag/m

In

65

U

COQ

u

LlI q:

IDl-

<

cc

LUCLZ

LUH

ON

CO

•H

<0QN3 33S/~1V3W

DSC

cooling

curve.

Category

I

film

(expanded

vertical

scale).

NORMALIZED

C2

<SET

15)

Rf^313865

SCAN:

IH

WTi

1.

14

tng

SCAN

RATE:

20.00

d«g/wln

66

<0QN3 33S/1V3W

TEMPERATURE

(C)
s;4*6<a
ei53

67

S

3

CJCOc

a

CJ a

COo

o

CO

I

I

! <0aN3 33S/1V3W

TEMPERATURE

CO

DSC

3.03

68

(J

COQu

UJ

q:ZDh-<

a:UJ

Q-

.•z LU1-

Fig.

10c.

DSC

cooling

curve.

Category

II

film.

ESU

69

U

cnau

LU

q:

IDH<

q;LU

CL2

LUH- I

Fig.

lOd.

DSC

cooling

curve.

Category

II

film

(expanded

vertical

scale

ra’E

70

U

cnQ

U

LU

a:3H

<

q:

LlI Q.

UJH

<0QN3 33S/Ivaw

Fig.

11a.

DSC

heating

curve.

Category

III

film.

as0

71

<00N3 33S/“1VGW

0)>

U

3

U

S’

•H

rj•y u

C/5 a

cc

•Hu<

TEMPERATURE

CO

DSC

3L83

72

<0QN3 33S/1V3W

TEMPERATURE

CO

0.5B

73

CJo

>

u

u

COc

oo

u

CJ

c/3 o

<0aN3 33S/1VJW

TEMPERATURE

CC)

DSC

00

•£

74

U

COQ

uV-/ u

q:3

h-

<

d:

lij Qu

H-

<OON3 33S/1VGW

Fig.

12a.

DSC

heating

curve.

Category

IV

film.

0.50

75

csj <0aN3 33S/1V3W

TEMPERATURE

CO

DSC

m'z

76

<00N3 3S/“1V3W

3

d

TEMPERATURE

(C)

DSC

0.50

77

<0aN3 G3S/nV3W

TEMPERATURE

CO

78

U

(nQ

u

txl CK

Z3

1—<

q:

LU

O-2

UJ

<0aN3 G3S/iy3W

Fig.

13a.

DSC

heating

curve,

B1

film.
1
NORMALIZED

FILM

5^367006

S03

SCAN;

1C

V/Tt

1.

00

mg

SCAN

RATEi

-20.00

dag/mln

79

0 <oaN3 33S/"1V3H

FlC*

13b.

DSC

cooling

curve,

B1

film.

80

0)

n

o£

o

co

o n

ffi n u

’a. Z

cc u Wi u < c

CCC W E

V- c c —

u o *--

r>. V- <r c>

*-* in u c

c ^ c

Of-* « O =tS: ^ o

u o

V.- c v:

‘luH

'OS'

t

t:h

81 - C E O • fH

4-1 *H «

fO *4-1 nj u <u

*>HU • U-. fo cu e O D f-H ^ *4-1 ‘H w o o y-i X <

Cl

W <U

(T3 ^ r3 J=

V4 fg

u i-J

J-. c. o U • OJ •H ^ i- w 2: r-1 O m c; cj •u i ^ rj w m c u- P3 vX u ^ oc D

i-* o C ^ O

O

O =te 4-* w c —

o r (T, v: E c ^ ^ c. X X c.

CL *4- w

C

in

cc o

82

(D

50

83

a

film

("311071).

(a)

Actual

film,

(b)

and

(c)

are

replica.*;

of

areas

on

opposite

surfaces

of

the

film.

84

CQ XJ D. Jw nj JZ 3

a. 4^

O W E GJ ^ a 03 ^ X

W kD

03 O i- o

r>- i- O X

C nO O <*n (J =?t ,

o: X r:

>

o

85

Fig. 19. Scanning Electron Micrograph of one of the

surfaces of Category I (#315420) film.

86

A

N

Y

020

i

-<M>-

-<M>-

Fig. 20. Wide angle x-ray diffraction patterns of Category

film (#315420). (a)' X-ray beam parallel to T.

(b) X-ray beam parallel to M. (c) X-ray beam

parallel to N.

200

87 A

N

Y

020

A

T

Y

020

1

-<M>-

Fig. 21. Wide angle x-ray diffraction patterns of Category II

film (//313865, gore 53). (a) X-ray beam parallel to

T. (b) X-ray beam parallel to M. (c) X-ray beam

parallel to N.
V

li '‘TTIIlllBiii ’ u ;

• ' . ' ft',

i’fe'S' !' V

'‘w.k

'll

'S -'Si

?n

Ui

W>

' iM

m Wm * 'Is

I :-'^

1 m.w

-<M>-

im

•y. • . , > .,' pp'l^

' S S|. Ui*i

’

i 1 7ilK£7)l

,:W?:

'k‘

ilM!

,•', 1

|V <i

i>Si T'', * f'1

• ‘.f V Ij

VI ..V M

'f *^'

'

'• I " ' '*3

. '

' tl

m

MfHB ' :.:[ ,,H' oi i»l]iwq' ,:, >K>'\

MK-< m

¥Wi .’cj: M

kii

it 71
88

A

T

020

-<M>-

Fig. 22. Wide angle x-ray diffraction patterns of Category III

film (#112877). (a) X-ray beam parallel to T. (b) X-ray beam parallel to M. (c) X-ray beam

parallel to N.
'

' .t e3 l^im^ irtil -

'F|fli43*^, tatiad {rf)

M o»

..AW?. .' ..' v.'*?\i?fli

ii ' >‘11. 4131

kii
89

-<M>- -<T>-

A

T

020

k

-<M>-

Fig. 23. Wide angle x-ray diffraction patterns of Category IV

film (#311071). (a) X-ray beam parallel to T.

(b) X-ray beam parallel to M. (c) X-ray beam

parallel to N.
"v-r^

' ry ft

i:-

\%» ^»q, . . cs^-

-

>'k'

' '’tv ^

i-jft
-<M>-

Fig. 24. Wide angle x-ray diffraction patterns of Bl film

(#367006). (a) X-ray beam parallel to T. (b) X-ray

beam parallel to M. (c) X-ray beam parallel to N.

91

b

c

Fig. 25. Schematic representation of two idealized microcrystal

orientations in a film. (a) The microcrystals are

oriented with the b-axis parallel to N, and the a-axis

(and hence the c-axis also) oriented randomly in the

MT plane. (b) The microcrystals are oriented with the

a-axis parallel to M, and the b-axis (and c-axis)

oriented randomly in the NT plane, (see text)
N

4 i «.• 0V« 1«> »«' JigiJts#44 5ri*ii»rii>a

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92

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«*4 O D. W ^ C OJ Q W s S -3

i-t ^ <y o • w •u ^ i-t O H4

O S U -u M

M 93 ? O U r-H

«3 S Ci Jd 3

<—* tn c cj Q *H -H O *H

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CM

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93

o

c

E

QJ

2

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4.* •H

1—1 03 c o 3

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a

1—1 . 03

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43 •Hn 1 iw 3- O W

<r 1—

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c on 43

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B

•H «c w

O Pm

0) X c

D. 03 m in a . o

CN o •> 44 4-1 c

o o

<D •H g w 4-1 •H V3 a

4-) <u 03

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(0

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(U (U U3 > •H 34

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03 T3 1 4-1 C

U3 3 CO 1—

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0) 0

43

(U m !> u CM (0

CM

GO

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o

(%) NIVaiS d33aD

squares

-

Cat.

I,

inverted

triangles

-

Cat.

II,

Cat.

Ill,

triangles

-

Cat.

IV.

94

o

c

E

LJ

2

I I

(0 CO iH 0) o fa u .fa CO

to e 3

cr £ (0 CO rH

•Hfa •H • M

t—

C

S O o

O w •H o fa tH CJ tH . CU

CO / fa Xi •H •H

(0 fa fa o CU o 3

u •H c '0- rC

0) rH U

e

'

' 3

•H e O CO

QJ fa 1 fa S (0 CO o rH

I—

o

o 33

fa fa G

o

OJ CO G (0 •H (0 3

fa (U (U fa fa

(0 fa o

3 CO

COfa X) 3

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S'? fa CU

V CO fa fa c c 33

•H CO

CO <U fa TD (0 fa 3 fa

10 CO (U>

fa u 10 (U

OJ o 3

3

fa CO fa CJ CN fa

00

<N

CO

•H

fa

(%) NlVdiS d33yD

Cat4

I,

inverted

triangles

-

Cat.

II,

circles

-

Cat.

Ill

triangles

-

Cat.

IV.
oor
o o o

CO TT CVJ

O

in

(O

in lO

in^/)

LxJ q:

»-vn

O

"q

-J

llJ in> o

inm

>iV 3 da IV Nivais % coo «s fH M 1 «3 . XI 4) (0 3 0

4.1 CJ o to 1 3 « 3 c n •H o (U S-i s 41 •H 0 a u

(U •H

M

Cua

«)M

<u . vO 41 41 3 3 U 3 0 O •H

4.1 e 1 w }.! 3

(0 OJ 3

0) CI- 4i

4i 3

41 S'S 3 U r-i c*

<3i

u

T3 o^

I—

(U (U

M

•H 41M 3

4i . U 41 3 C 3 U •H CJ 3

0) 1 > 4) ca W3

fO<u . CO u 3

XJ 0 3

•H

4J 0 3 3 r'-1 41 c 1 T3- .H 41 3 3 3 4J

4i 3

41 E 3 » >

•H 3

S'? 4-1 •H

a^

CN

CO

Cat.

TV,

crosses -

Cat.

B1

95

Fig. 30. An example of biaxially oriented film under inflation.

96

CO QCO

CO

UJ

orCO

C\JO

N0liV9l\l013 %

Fig.

31.

Failure

envelope

at

23°C

for

linear

polyethylene

with

=

15,300

and

=

99,000.

Log

percent

elongation

versus

engineering

stress

for

various

isochrones

obtained

from

uniaxial

creep

data.

Line

a

corresponds

to

necking

and

line

to

fracture.

ELONGATION

97

Fig. 32. Failure envelope at 23°C for linear polyethylene with - 15,000 and = 160,000. Log percent elongation versus

engineering stress for various isochrones obtained fron

uniaxial creep data. Line a corresponds to necking, line 6 to

the fully necked condition, and T to fracture.
,'S7

: ;/

•«rj» ti),

'M 'ifh:

K-e,

itf ->te-

'•a^‘

/tisl.lj 1

m.

<v.

*C>.

:^:li w#: t

I'M

!LS i" %

D

V .

s I

VkfW.'

4»i.i

i.’i. .'ir 0/

?'*-^'a

I:?;'!'

.T4...

[;;

^ or

,. h{*(u\!?M> 223»T8 -ir ^

, , iw

^.,: VS '’:p;u

-.*rwi^ ‘ • *1^

•TBliil ,.St .sllS ' ^ -4- £_• : ' nm^ - ids . V .f! 3*c^ i$' •qoXttfw

i>oi«>*S3(tOil*f i'WOW<| :'»W' 4000,0d.r -

80^0'1'W' .‘3pT^M;«rtty,ft

«<

II

'

ei'-i
ELONGATION

98

10 20 30

STRESS (MPa)

Fig. 33. Failure envelope at 23°C for linear polyethylene with - 15,600 and = 192,000. Symbols have the same meaning as in

Fig. 24.
1

wailtl

0(v.),5:e{ * «ir‘

'

JO,'’! » nM

1

%

t

/

»

\

I

\

»

i

)

1

\

\

I
uws.lliA »^ev- u S Of’T. 0^ COMM. 1. PUBLICATION OR 2. Performing Organ. Report No. 3. Publication Date

PIBLiOGRAPHIC DATA

REPORT NO.

NBSIR 84-2989 March 1985

SHEET iSee instructions! . title and subtitle

The Structure and Properties of Polyethylene Films Using in

Heavy Lift Balloons

5. AuTHOR(S) Khoury, J. M. Crissman, B. M. Fanconi, H. L. Wagner, L. H. Bolz,

and C. A. Harding

6. PERFORMING ORGANIZATION (If joint or other than N BS, see instructions) 7. Contract/Grant No.

national bureau of standards

department of commerce

WASHINGTON. D.C. 20234

NASA Order 5Q1834D

8. Type of Report & Period Covered

NBSIR - Jan. - May 1984

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City, State, ZIP)

NASA Goddard Space Flight Center, Wallops Flight Center, Wallops Flight Facility,

Balloon Projects Branch, Wallops Island, VA 23337

10.

SUPPLEMENTARY NOTES

I

I Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most si gnificant information. If document includes a si gnificant

bibliography or literature survey, mention it here)

The following features of five polyethylene films used by NASA in the construction

of heavy lift balloons have been examined: molecular weight, molecular weight

distribtuion, branching, melting behavior, density, surface texture, birefringence,

orientation of crystalline regions, uniaxial deformation in the machine and

transverse directions, and the effect of sample geometry and strain rate on

deformation behavior. The goal of this exploratory study was to determine whether

there are significant differences in any of the above mentioned features, or^

combination of features between the films. The acquisition of such information is

a first step towards determining whether there are any specific correlations

between film characteristics and the incidence of catastrophic failure of balloons

during ascent through the troposphere. This exploratory study has resulted in the

identification of similarities and differences between various features of the

films. Close similarities have been found in methyl group content, crystallinity,

and peak melting temperature. The preferred orientations in the crystalline regions

appear to be qualitatively similar or related. Differences among the films have

been revealed in two features, namely between their molecular weights, and in the

balance of the strain to break behavior in the machine direction relative to that

in the transverse direction.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words tv iem.co on»- Balloon film; branching; mechanical properties; molecular weight j distribution; morphology; orientation; polyethylene i

13. AVAILABILITY 14. NO. OF I prin'^e:. k- .

•

Unlimited

I I For Official Distribution. Do Not Release to NTIS

(Lj] Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

^ 20402.

[3] Order From National Technical Information Service (NTIS), Springfield, VA. 22161