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LIBRARY ,

' Michigan State
,1 University

 

 

This is to certify that the

thesis entitled

Evaluation of Parameters Impacting the Permeability of a
Fragrance Delivery System

presented by

Hojoon Lee

has been accepted towards fulﬁllment
of the requirements for

Masters degree in Packaging

 

 

rm

Major prth’essor

Date November 6, 1996

 

0.7639 MS U is an Afﬁrmative Action/Equal Opportunity Institution

 

PLACE It RETURN BOX to remove thie checkout horn your record.
TO AVOID FINES return on or before date due.

DATE DUE DATE DUE DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

MSU le An Affinnetiw Action/Emu Opportunity lnetituion
Wane-m

EVALUATION OF PARAMETERS IMPACTING THE PERMEABILITY OF A

FRAGRANCE DELIVERY SYSTEM

By

Hojoon Lee

A THESIS

Submitted to
Michigan State University
in partial fulﬁllment of the requirements
for the degree of

MATER OF SCIENCE

School of Packaging
1 996

ABSTRACT

EVALUATION OF PARAMETERS IMPACTING THE PERMEABILITY OF A
FRAGRANCE DELIVERY SYSTEM

BY
Hojoon Lee

The permeation of selected fragrance volatiles through an ethylene-vinyl
acetate copolymer (EVA) membrane based fragrance delivery system was
studied by an isostatic procedure at 50°C and a constant air ﬂow rate of 20
cclmin, to insure that the mass transport process is diffusion controlled. The
permeation rates of the fragrance volatiles, linalool, phenethyl alcohol, benzyl
acetate, and a-hexyl cinnamaldehyde, were determined as a function of time.
Variables evaluated in a three level, three variable statistical design experiment
included the vinyl acetate content of the EVA membrane the thickening agent
and‘dispersing solvent contents of the fragrance formulations. Statistical
analysis showed that the vinyl acetate content of the test membranes was a
signiﬁcant variable effecting the permeation rates of fragrance volatiles through
the fragrance delivery system. Film A(vinyl acetate content 6.5%) was found to
have signiﬁcantly lower transmission rates for the respective probe compounds
when compared to Film B(vinyl acetate content 9%) and Film C(vinyl acetate

content 12%).

DEDICATION

This thesis is dedicated to my parents, brother and sister who encouraged
and support my graduate education.

Without their endless patience and support, it is hardly possible to
complete my graduate education. Special thanks to my father who gave me

endless faith, patience and the idea that I can do.

ACKNOWLEDGMENTS

I would like to express a great deal of thanks to Dr. Jack Giacin for his
guidance, and support an patience for serving as my adviser. Appreciation is
also expressed to Dr. Hugh Lockhart and Dr. Ivan Mao for serving my committee.
A special thanks to Mr. Greg Chamber for giving me a chance to take this
project.

Acknowledgment is also given to the Dial Corporation for ﬁnancial support an

providing the necessary materials for this study.

iv

TABLE OF CONTENTS

List of Tables .................................................................................... vii
List of Figures ................................................................................... xi
Nomenclature ................................................................................... xx
INTRODUCTION ............................................................................... 1
LITERATURE REVIEW ,

Permeation of organic vapor mixtures through polymer

membrane ............................................................................... 4
Theory: liquid permeation ........................................................... 8 _
Binary liquid permeation ............................................................. .10
Factors affecting permeation ....................................................... 12
Temperature ............................................................................ 1 3
The nature of perrneant .............................................................. 14
Nature of polymer ..................................................................... 17
Concentration ........................................................................ 20
Permeation measurement : organic vapor permeation ..................... 20
MATERIALS AND METHODS
Blister tray and ﬁlm samples ....................................................... 22
Fragrance formulations ............................................................... 22
Probe compounds ........... ° .......................................................... 24
Methanol absolute ..................................................................... 27

Nitrogen - carrier gas .................................................................. 27

Andex laboratory blister sealer ...................................................... 27

Analytical methods ...................................................................... 28

Permeation measurements ........................................................... 29

Mass balance studies .................................................................. 33

Statistical analysis ..................................................................... 36
RESULTS AND DISCUSSION

Vapor pressure and vapor activity of the

fragrance formulation .................................................................. 38

The permeation studies of fragrance volatiles ........ I ......................... 42

Statistical analysis ..................................................................... 1 13
SUMMARY AND CONCLUSIONS ......................................................... 114
FUTURE RESEARCH ........................................................................ 117
APPENDICES

A - Gas chromatograph calibration procedures ............................... 118

B - Vapor pressure and vapor activity ............................................ 125

C - Data on the transmission rates of the probe volatiles from-fragrance

formulation 1-9 through ﬁlm A, ﬁlm B, and ﬁlm C at 50°C ............. 127

D - Statistical analysis ............................................................... 154

E - Melt proﬁle of ﬁlm samples ................................................... 160
BIBLIOGRAPHY ................................................................ ‘ ............... 162

vi

Table

10.

11.
12.
13.
14.
15.

LIST OF TABLES

Title Page NO.

Fragrance formulations ............................................................. 24
Statistical design of the study ..................................................... 35
Saturation vapor pressure of probe compounds

at 50°C (mmHg) ...................................................................... 39
Vapor pressure of probes in the fragrance formulations

at 50°C (mmHg) ...................................................................... 39
Vapor activity of probes in fragrance formulations .......................... 40

The concentration of the probe compounds (glml)
in the fragrance formulations ..................................................... 41
Global loss or the total volatiles loss from fragrance formulations

through ﬁlm A, ﬁlm B, and ﬁlm C ................................................ 43
Percent loss of speciﬁc probe compounds from fragrance formulation
through ﬁlm A ........................................................................ 44
Percent loss of speciﬁc probe compounds from fragrance formulation
through ﬁlm B ........................................................................ 45
Percent loss of speciﬁc probe compounds from fragrance formulation
through ﬁlm C ........................................................................ 46
Calibration data for IinanoI ....................................................... 121
Calibration data for phenethyl alcohol ......................................... 121
Calibration data for benzyl acetate ............................................. 122
Calibration data for a-hexyl cinnamaldehyde ................................ 122

Flux (g/day) x E-2 as a function of run time for probe compounds from
fragrance formulation #1 through ﬁlm A at a cell ﬂow rate of 20cclmin
at 50°C ................................................................................. 127

vii

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

Flux (glday) x E-2 as a function of'run time for probe compounds from
fragrance formulation #2 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 128
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #3 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ....................... . .......................................................... 129
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #4 through ﬁlm A at a cell flow rate of 20cclmin

at 50°C ................................................................................. 130
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #5 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 131
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #6 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 132'
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #7 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 133
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #8 through ﬁlm A at a cell flow rate of 20cclmin

at 50°C ................................................................................. 134

Flux (glday) x E-2 as a function of run time for probe compounds from

fragrance formulation #9 through ﬁlm A at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 135
Flux (glday) x E-2 as a function of run time for probe compounds from

fragrance formulation #1 through ﬁlm B at a cell ﬂow rate of ZOcclmin

at 50°C ................................................................................. 136
Flux (glday) x E-2 as a function of run time for probe compounds from

fragrance formulation #2 through ﬁlm 8 at a cell flow rate of ZOcdmin

at 50°C ................................................................................. 137

viii

36.

37.

38.

39.

40.

41.

42.
43.

Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #4 through ﬁlm C at a cell ﬂow rate of 20cclmin

at 50°C .............................................................................. 148
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #5 through ﬁlm C at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 149
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #6 through ﬁlm C at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 1 50
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #7 through ﬁlm C at a cell ﬂow rate of ZOchmin

at 50°C ................................................................................. 1 51
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #8 through ﬁlm C at a cell ﬂow rate of 20cclmin

at 50°C ................................................................................. 152'
Flux (glday) x E-2 as a function of run time for probe compounds from
fragrance formulation #9 through ﬁlm C at a cell ﬂow rate of ZOGCImin

at 50°C ................................................................................. 153
Slope of transmission proﬁle curve ............................................. 155
Results of analysis of variance ................................................... 156

Figure Title Page NO.
1. Fragrance delivery system ...................................................... 23
2. Schematic of fragrance delivery system

permeation test apparatus ...................................................... 31
3. Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 50
4. Transmission proﬁle of phenethyl alcohol through a ﬁlm A from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 50
5. Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 51
6. Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 51
7. Transmission proﬁle of phenethyl alcohol through a ﬁlm A from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 52
8. Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 52
9. Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 53
10. Transmission proﬁle of phenethyl alcohol through a ﬁlm A from

fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 53
11. Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #3 at 50°C and ﬂow rate of ZOcdmin ............ 54
12. Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 54
13. Transmission proﬁle of phenethyl alcohol through a ﬁlm A from

fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 55
14. Transmission proﬁle of benzyl acetate through a ﬁlm A from

LIST OF FIGURES

xi

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

28.

29.

fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 55
Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #5 at 50°C and flow rate of 20cclmin ............ 56
Transmission proﬁle of phenethyl alcohol through a ﬁlm A from
fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 56
Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 57
Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin ............ 57
Transmission proﬁle of phenethyl alcohol through a ﬁlm A from
fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin ............ 58
Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #6 at 50°C and ﬂow rate of 20¢clmin ............ 58
Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin ............ 59
Transmission proﬁle of phenethyl alcohol through a ﬁlm A from
fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin ............ 59
Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin ............ 60
Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 60
Transmission proﬁle of phenethyl alcohol through a ﬁlm A from
fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 61
Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 61
Transmission proﬁle of linalool through a ﬁlm A from

fragrance formulation #9 at 50°C and ﬂow rate of 20¢c/min ............ 62
Transmission proﬁle of phenethyl alcohol through a ﬁlm A from
fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 62
Transmission proﬁle of benzyl acetate through a ﬁlm A from

fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 63

xii

30.

31.

32.

33.

34.

35.

36.

37.

38.

39.

40.

41.

42.

43.

45.

Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 63
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #1 at 50°C and ﬂow rate of ZOcc/min ............ 64
Transmission proﬁle of benzyl acetate through a ﬁlm 8 from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 64
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 65
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 65
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 66
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 66
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 67
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 67
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #4 at 50°C and ﬂow rate of 200dmin ............ 68
Transmission proﬁle of phenethyl alcohol through a ﬁlm 8 from
fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 68
Transmission proﬁle of benzyl acetate through a ﬁlm B from *
fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 69
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 69
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 70
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 70
Transmission proﬁle of linalool through a ﬁlm 8 from

xiii

46.

47.

48.

49.

50.

51.

52.

53.

54.

55.

56.

57.

58.

59.

60.

fragrance formulation #6 at 50°C and ﬂow rate of 200dmin ............ 71
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #6 at 50°C and ﬂow rate of 200clmin ............ 71
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #6 at 50°C and flow rate of 20cclmin ............ 72
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #7 at 50°C and flow rate of 20cclmin ............ 72
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin ............ 73
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #7 at 50°C and ﬂow rate of ZOCCImin ............ 73
Transmission proﬁle of linalool through a ﬁlm B from

fragrance formulation #8 at 50°C and flow rate of 20cclmin ............ 74
Transmission proﬁle of phenethyl alcohol through a ﬁlm B from
fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 74
Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 75
Transmission proﬁle of linalool through a ﬁlm 8 from

fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 75
Transmission proﬁle of phenethyl alcohol through a ﬁlm 8 from
fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 76

- Transmission proﬁle of benzyl acetate through a ﬁlm B from

fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 76
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin ............ 77
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #1 at 50°C and ﬂow rate of ZOcclmin ............ 77
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #1 at 50°C and flow rate of ZOcclmin ............ 78
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 78

xiv

61.

62.

63.

64.

65.

66.

67.

68.

69.

70.

71.

72.

73.

74.

75.

76.

Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 79
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin ............ 79
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #3 at 50°C and ﬂow rate of 200clmin ............ 80
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #3 at 50°C and flow rate of 20cclmin ............ 80
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin ............ 81
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 81
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 82
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin ............ 82
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 83
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 83
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin ............ 84
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin ............ 84
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from I
fragrance formulation #6 at 50°C and ﬂow rate of 200dmin ............ 85
Transmission proﬁle of benzyl acetate through a ﬁlm C from

fragrance formulation #6 at 50°C and flow rate of 20cclmin ............ 85
Transmission proﬁle of linalool through a ﬁlm C from

fragrance formulation #7 at 50°C and flow rate of 20cclmin ............ 86
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from

XV

77.

78.

7.9.

80.

81.

82.

83.

85.

86.

87.

88.

89.

fragrance formulation #7 at 50°C and flow rate of 20cclmin ....... ' ..... 86
Transmission proﬁle of benzyl acetate through a ﬁlm C from
fragrance formulation #7 at 50°C and flow rate of 20cclmin ............ 87
Transmission proﬁle of linalool through a ﬁlm C from
fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 87
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin ............ 88
Transmission proﬁle of benzyl acetate through a ﬁlm C from
fragrance formulation #8 at 50°C and ﬂow rate cf 20cclmin ............ 88
Transmission proﬁle of linalool through a ﬁlm C from
fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 89
Transmission proﬁle of phenethyl alcohol through a ﬁlm C from
fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin ............ 89
Transmission proﬁle of benzyl acetate through a ﬁlm C from
fragrance formulation #9 at 50°C and ﬂow rate of 200dmin ............ 90
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #1) ......... 92
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #1) ...................................................... 92
Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle

(fragrance formulation #1) ...................................................... 93
Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #2) ......... 93
Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #2) ...................................................... 94
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
benzyl acetate vapor transmission proﬁle

(fragrance formulation #2) ...................................................... 94

xvi

90. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

linalool vapor transmission proﬁle (fragrance formulation #3) ......... 95
91. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #3) ...................................................... 95
92. Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;

benzyl acetate vapor transmission proﬁle

(fragrance formulation #3) ...................................................... 96
93. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

linalool vapor transmission proﬁle (fragrance formulation #4) ......... 96
94. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #4) ...................................................... 97
95. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

benzyl acetate vapor transmission proﬁle

(fragrance formulation #4) ...................................................... 97
96. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

linalool vapor transmission proﬁle (fragrance formulation #5) ......... 98
97. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #5) ...................................................... 98
98. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

benzyl acetate vapor transmission proﬁle

(fragrance formulation #5) ...................................................... 99
99. Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;

linalool vapor transmission proﬁle (fragrance formulation #6) ......... 99
100. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #6) ...................................................... 100
101. Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;

benzyl acetate vapor transmission proﬁle

xvii

102.

103.

104.

105.

106.

107.

108.

109.

110.

111.

112.

(fragrance formulation #6) ...................................................... 100
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #7) ......... 101
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #7) ...................................................... 101
Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle

(fragrance formulation #7) ...................................................... 102
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #8) ......... 102
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #8) ...................................................... 103
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
benzyl acetate vapor transmission proﬁle

(fragrance formulation #8) ...................................................... 103
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #9) ......... 104
Comparison of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle

(fragrance formulation #9) ...................................................... 104
Comparison of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
benzyl acetate vapor transmission proﬁle

(fragrance formulation #9) ...................................................... 105
Relative concentration of linalool permeated through ﬁlm A, ﬁlm 8,

and ﬁlm C permeated from fragrance formulation #2 at 50°C and

ﬂow rate of 20cclmin ............................................................ 106
Relative concentration of phenethyl alcohol permeated through ﬁlm A,
ﬁlm B, and ﬁlm C permeated from fragrance formulation #5

at 50°C and ﬂow rate of 20cclmin .......................................... 106

xviii

113.

114.
115.
116.
117.
118.

119.

120.

Relative concentration of benzyl acetate permeated through ﬁlm A,
ﬁlm B, and ﬁlm C permeated from fragrance formulation #8

at 50°C and ﬂow rate of 20cclmin .......................................... 107
Calibration curve for linalool. .. ............................................. 123
Calibration curve for phenethyl alcohol .................................... 123
Calibration curve for benzyl acetate ....................................... 124
Calibration curve for alpha-hexyl cinnamaldehyde ..................... 124

Comparison of barrier characteristics of ﬁlm content

(linalool) ........................................................................... 157

Comparison of barrier characteristics of ﬁlm content

(phenethyl alcohol) ............................................................ 1 58

Comparison of barrier characteristics of ﬁlm content

(benzyl acetate) ............................................................... 159
NOMENCLATURES

xix

AH

Mc

QA.Qe
QO

QA.Qe

Vs
XA.Xa

X1
pa

NOMENCLATURES

Concentration of penetrant in purely amorphous polymer
Solubility of liquid in the polymer

Diffusion coefﬁcient
Constant; Diffusivity at zero concentration of liquid

Activation energy for the diffusion
Heat of fusion
Heat of solution

Average molecular weight of the amorphous chain segment in the
presence of a penetrant '
Permeability coefﬁcient

Permeation rates of component A and B in binary mixture
Total permeation rate of an ideal binary mixture

Total permeation rate of a mixture
Permeation rates of pure components A and B

Solubility coefﬁcient

Molar volume of penetrant
Weight fraction of A and B in the perrneant

Flory-Huggins interaction parameter
Density of amorphous polymer

Constant; a measure of the plasticizing action of the liquid on the

membrane

a - Separation factor
8 - Permeation ratio

8A,63 - Permeation ratios of components A and B

mraooucrrou

Packaging requirements often include a need to retain volatile contents
within a package, or to prevent atmospheric vapors from entering a package.
Such needs were usually easily handled by glass or metal containers. Because
of a multitude of reasons, many economic, one would like to use lighter and
disposable ﬂexible packaging. Product vapors of concern are often organic and
can include ﬂavor ingredients in foods, as well as active ingredients in medical, -
household, and industrial products. Environmental vapors to be kept out of
products include those of motor fuels, detergents, solvents, etc.

The selection of ﬂexible packaging polymer ﬁlms for the aforementioned
applications requires more information than is normally available from resin and
ﬁlm suppliers. A quantitative knowledge of permeation rates, exposure
conditions, and limits of acceptability allows one to optimize multilayer ﬁlms and
Iaminations, with respect to cost and performance.

' The transport of non-interactive penetrant molecules such as ﬁxed gases
through polymeric materials has been studied in great detail (Chem 913.11,, 1983;
Crank and Park, 1968; Pasternak ,et_a_l_., 1970; Pye et_al_._, 1976; Stannett gal,
1972). However, studies involving the permeation of organic vapors and liquids
have been limited, and have focused primarily on single component organic
vapor/polymer systems. Studies which have been published describing the
permeation of organic vapors and liquids through barrier polymer include those

by Rogers et al.,1960; Rogers,1964; Niebergall et al.,1978; Zobel,1982; Baner et

al.,1986; Hernandez et al.,1986; Liu et al.,1986; and Mohney et al.,1988. These
studies were very important in providing a better understanding of the
mechanism of the permeation process involving organic perrneants. However,
only a limited number of studies have been reported on the permeation of multi
component mixtures of organic liquids and vapors through barrier membranes.
The lack of data can be attributed to the complexities involved with organic
vapors exposed to plastics.

In permeability studies reported by Michelson et al. (1985), it was found
that for binary organic liquid mixtures of varying composition, three possible
modes of interaction between the components of the mixture and the polymer
could be described, namely :

1. The mixture may decrease the lag time or break through time of the

individual components.

2. A component that does not permeate as a pure liquid may be

transported through the membrane by another component, when present

in the mixture.

3. The collective permeation rate for the mixture may be higher than the

transmission rate of either pure component of the mixture.

The present study will focus speciﬁcally on determining the permeability of
volatile compounds of a multi-component organic fragrance formulation through
semi-permeable polymeric ﬁlms, and the effect of formulation and barrier ﬁlm
composition on the transport process.

The objectives of this study are :

1. Carry out permeability studies with a multi-component organic fragrance
formulation; Evaluate the following variables and the effect of membrane
composition and formulation composition on the permeability of fragrance probe
volatiles through the fragrance delivery system membrane.
2. Design and assembly of a test system to determine the permeability of the
constituents of a multi-component organic fragrance mixture through a barrier
ﬁlm. The cell assembly will be designed to accommodate the fabricated
fragrance delivery system, and will allow for measurement of the permeation rate
as a function of time.
3. Carry out permeation studies with multi-component organic fragrance
formulations and evaluate the effect of formulation variables and barrier ﬁlm
composition on the transport of the selective individual penetrants through the
test polymer structure.
4. Perform statistical analysis on the permeability data to establish the
signiﬁcance of the respective test variables and the interaction terms associated
with the permeability of volatiles through the fragrance delivery system.

. In terms of theoretical importance, a better understanding of the effect
of penetrant/polymer interaction on the transport properties of individual

components of a multi-component organic vapor mixture will be obtained.

LITERATURE REVIEW

PERMEATION OF ORGANIC VAPOR MIXTURES THROUGH POLYMER
MEMBRANE

The barrier properties of different materials against various liquids, gases,
and vapors are of paramount importance in packaging applications. The
permeability of plastic ﬁlms and other packaging materials to gases and vapors
is of great practical interest.
In particular, knowledge of the permeability of organic vapors is needed for the
successful design of packaging to prevent deterioration in product quality due to
excessive loss or gain of such penetrants during storage. The transport of non--
interactive penetrant molecules such as ﬁxed gases through polymer materials
has been studied thoroughly. However, studies involving the permeation of
organic vapors and liquids have been limited, and have focused primarily on
single component organic vapor/polymer systems. Studies which have been
published describing the permeation of organic vapors and liquids through
barrier polymers provide a better understanding of the mechanism of the
permeation process involving organic perrneants. However, only a limited
number of studies have been reported on the permeation of multi-component
mixtures of organic liquids and vapors through barrier membranes due to the
complexities involved with organic vapors exposed to polymers membranes.

Studies involving the permeation of organic vapors have been limited, and

have focused mainly on single component organic vapor/polymer systems.

Published studies describing the permeation of organic vapors through barrier
polymer include those by Rogers gt_a_l., 1960; Gilbert _et_a_l., 1983; Niebergall gt
al., 1978; Zobel,1982; Rogers,1964; Baneret_a_l., 1986; Liu gal, 1986
Hernandez 32111., 1986; Hatzidimitriu _et_a_l., 1987, Mohney et_al., 1988; Schaper,
1989, Rodney gal, 1992, and Johansson 11L, 1994. These studies were
valuable to provide a better understanding of the mechanism of the permeation
process involving organic perrneants. However, only a limited number of studies
have been reported on the permeation of multi-component mixtures of organic
vapors through barrier membranes (Li gig, 1965; Huang and Lin,1968;
Tombalakian, e131,, 1972, Fels, 1972, Weinberg, 1976; Michelson gt_a_l., 1985;
Hensley Lain 1991, Theodorou, gal, 1992). Because of the complexities
involved with organic vapors exposed to plastics, there are few data about the
permeation of multi-component organic vapor. Hensley gt_a_l. (1991) reported on
the concentration dependency of the permeability of organic vapor mixtures, and
the effect of the relative concentration of individual components of the vapor
mixtures on the transport of each particular penetrant comprising the mixture.
Stannett and Yasuda (1963) have reported that with most organic vapors, the
permeability increases rapidly with increasing vapor pressure. The permeability
to liquid penetrants is considerably greater than with the corresponding saturated
vapor. However, at lower vapor activity, the effect of vapor mixtures on the
permeation and diffusion of the individual components of the vapor mixture is

unpredictable.

Ghosh (1982) has studied the sorption characteristics of vapor of pure
hydrocarbons and their binary mixtures in low density polyethylene, under
various conditions of temperature and pressure. In order to compare the
plasticizing effects of various hydrocarbons, Ghosh calculated the average
molecular weigh of an amophorous chain segment in the presence of a
penetrant within the polymer network (Me) by using the method of Baddour gig];

(1964). This relationship gives:

C* l 1
)mrIn<1+C*)+(1+C*)+x1(1+C*)2}" <1)

 

 

 

 

Mc=VsPa(1+C*

where C* is the concentration of penetrant in purely amorphous polymer, in
cm3/cm3; Vs is the molar volume of the penetrant, cm3lmole; p. is the density of
purely amophorous polymer in g/cm3, and X1 is the Flory-Huggins interaction
parameter. Mc increases with vapor activity, i.e., increase in pressure and [or
decrease in temperature.

The sorption in a semicrystalline polymer like low density polyethylene is
dependent upon two factor: (a) temperature, which changes the amorphous
content of the polymer and penetrant mobility; and (b) penetrant concentration,
which brings about further changes within the amorphous polymer chain net
work. The equilibrium sorption characteristics are very sensitive to temperature
and pressure. The study showed that sorption increased with temperature and
vapor activity. The increase being relatively slow at the initial stages and rapid

subsequently, which is explained by Doolittle’s theory of plasticization (Doolittle,

1954). The plasticization action in a noncrosslinked polymer like polyethylene
mainly consists of reducing the number of pure mechanical entanglements of the
amorphous chain segments between crystallites (Baddour et_a_rl., 1964; Ritchie,
1972).

Hensley gtjll (1991) studied the concentration dependency of the binary organic
mixture, limonene - ethyl acetate through biaxially oriented polypropylene ﬁlm.
The results showed that the collective permeation rate for the mixture was
signiﬁcantly higher than the transmission rates of the pure components, showing
a synergistic effect. At lower activity levels, the presence of limonene vapor
resulted in a dramatic increase in the transport properties of the co-perrneant,
ethyl acetate. At the highest vapor activity studied, ethyl acetate was found to .
signiﬁcantly increase the transport properties of limonene, as compared to the
permeability of pure limonene at similar activity levels.

DeLassus and Strandlburg (1991) studied the permeation of a mixture of organic
vapors They observed both a slight decrease in the permeability of ethyl-2-
methylbutyrate and a slight increase in the permeability of trans-2-hexenal and
hexanal while an apple ﬂavor compounds, when permeated as a mixture through
low density polyethylene, at a very high concentration.

Theodorou gig; (1992) determined the permeability coefﬁcients (P) of linalool,
citral, ethyl butyrate, d-limonene and octanal through LDPE and ionomer ﬁlm,
when measured alone as individual perrneant and as a component of a mixture

at a temperature of 23°C and in saturated water vapor.

Generally, the permeability, diffusion and solubility coefﬁcient (P, D, and S)
values for perrneants. measured in a mixture, were substantially less than the
values obtained for the individual penetrants. Permeability behavior of these
compounds, at low concentrations in the mixtures, was similar to that of
perrneant vapors. Reduction of the solubility coefﬁcient for a permeation mixture
was greater with penetrants with higher solubility coefﬁcient values. Selected
compounds in the mixture showed an increase in permeability coefﬁcient values,
which was attributed to high vapor concentration levels. However, a reduction in
the permeability coefﬁcient value with mixtures seem to indicate that
plasticization or swelling of the polymer motion by the vapor mixture is not
occurring at these low penetrant concentrations. The reduction in permeability is
thought to be caused by the increase in competition for sorption and diffusion
sites in the presence of other compound similar to the penneant gases. The
reduction in permeability of a perrneant gas in the presence of a second
perrneant gas such as C02 and CH4 has been explained, based on competitive

sorption and diffusion models (Story et al., 1989).

THEORY
LIQUID PERMEATION

Permeation normally occurs when a gas or organic vapor comes in
contact with a polymer. Permeation is the ﬂow of a vapor from one chemical
potential to a lower level through a matrix. The rate of permeation through a

polymer membrane depends on the penetrants solubility and diffusivity in the

polymer. The steady state permeation process may be simply described by
F ick’s law:

Q = -D I (dcldx) (2)
where O is the permeation rate, D is the diffusion coefﬁcient, and dcldx is the
concentration gradient across the membrane. The value of D depends strongly
on the concentration of perrneant liquid in the polymer membrane. An equation
which is commonly used to relate D to the solubility of a liquid in the membrane
and to a diffusivity Do , obtained at zero concentration of liquid is:

D = D,,e‘"3 ( McCall,1957; Chandler and Henley, 1961) (3)
where Do and y are constant at a given temperature. The constant 7, is a
measure of the plasticizing action of a liquid on _the polymer membrane; the
concentration c of liquid in the polymer is the amount of sorption of liquid in the
polymer, which is essentially determmed by the solubility of the liquid in the
polymer. Therefore, equation(3) shows that in the permeation process the
diffusivity of a liquid is actually a function of its solubility in the polymer
membrane.

Substituting eq.(3) in eq.(2), rearranging, and integrating with boundary
condition gives:

QIédx=~Do Iﬁ§e7°dc (4)
where L is the thickness of the membrane, c1 and c; are the concentrations of

perrneant in the polymer at the upstream and downstream surfaces, respectively.

At steady state, the permeation rate can be expressed as

10

Q = (Do/m (ef‘ - e“) (5)
where 01 can be determined by the equilibrium sorption of liquid in the polymer
and c; is essentially zero, provided the downstream cell chamber is maintained
at a low perrneant partial pressure, and the rate of evaporation of permeate is
not controlled by diffusion.

Equation (5) can then be simpliﬁed to

Q = (Do IyL) (em - 1) (6)
where C8 is the solubility of the liquid in the polymer membrane. This equation
shows that the permeation rate of a liquid through a polymer membrane depends
not only onits diffusivity, but also on its solubility in the membrane (Huang and

Lin, 1968)

BINARY LIQUID PERMEATION

The membrane selectivity of a binary system consisting of two liquids A
and B can be expressed in terms of a separation factor a, deﬁned as the
concentration ratio BIA of the perrneants in the downstream, divided by the
concentration ratio BIA of the penneants in the upstream.

ae/A=(Ye/YA)/(Xe/XA) (7)

where XI and X3 are the weight fractions of downstream A and B in the
penneant upstream mixture, while YA and Y3 are the weight fractions of A and B
in the permeate.

The total permeation rate (Q) of a mixture through a polymer membrane

is:

11

Q = 9A 1' <18 (8)
where qA and q3 indicate the permeation rates of components A and B in the
binary mixture.

If the permeation process is ideal, the transmission rate of the mixture can
be expressed in terms of the pure component permeation rates as:

qu = XAQA (9)

908 = X308 (10)
where Q is the permeation rate of the individual components and the superscript
zero refers to the ideal permeation rate. The total ideal permeation rate Q° is
given by

Q°=XAQA+(1'XA)QB (11).
and the selectivity for a system which exhibits ideal behavior is simply the ratio of
the pure component permeation rates. (Huang and Lin, 1968)

(1°31. = 08 I 0,. (12)
Stannett (1962) and Rogers (1965) found that perrneant gas and mixtures exhibit
such ideal behavior. Non-ideal behavior results when on component of the
permeating mixture plasticizes the membrane to a greater extent than the other.
Organic vapors or liquids do not exhibit ideal permeation behavior because the
perrneants swell the membrane to different degrees. The measure of the non-
ideal behavior of the permeation of liquid mixtures can be expressed by a
permeation ratio 8, deﬁned as the ratio of the actual permeation rate Q and its
ideal permeation rate 0°.

0=QIQ° (13)

The permeation ratios for the individual Components can be expressed as

9A = all I GA (14)
and

93 = qg / QB (15)
where 9A and 03 are the permeation ratios of components A and B, qA and qa are
the permeation rates of components A and B in the binary mixtures and QA and
03 are the permeation rates of pure components A and B respectively.

Thus the permeation ratio should be equal to unity when a system exhibits
ideal permeation behavior. The value of the permeation ratio may be higher or
lower than unity for non-ideal permeation. If the permeation ratio of a system is
higher than unity, the system can be said to exhibit a permeation enhancement

effect, while a value lower than unity indicates a permeation depression effect.

FACTORS AFFECTING PERMEATION

Some of the principal factors affecting the rates of permeation are:

0 Temperature

. The nature of the penneant, including molecular size, shape

. The nature of the polymer, including morphology and molecular motion of
the polymer

. The penetrant concentration (Rogers et al., 1962)

I3

TEMPERATURE

For the mass transfer process described by Fick’s ﬁrst and second Laws
of diffusion, permeation is the ﬂow of a vapor from one chemical potential to a
lower level through a matrix. The process involves several steps, the slowest of
which is usually movement through the non-crystalline regions of the polymer.
The perrneant molecules are able to diffuse through the polymer matrix by
“jumping” from one sorption site to the next, under a pressure gradient. The
amorphous sections of the polymer, or the free volume, create the “holes or
microvoids” required to accommodate a penneant molecule, and enough holes
must be present to create a channel or pathway to allow for successful
diffusional jumps. In general, the temperature dependence of P, D, and S are .

given by the Arrehenius relationships:

D = Do exp (-EDIRT) . (16)
S = So exp (-AH/RT) (17)
P = P0 exp (-Ep/RT) (18)

where D is the diffusion coefﬁcient, S is the solubility coefﬁcient, and P is the
permeability constant. AH is the heat of solution, ED and Ep are the activation
energies for the diffusion and permeation processes, and P0 = 0080,
For easily condensable vapors, AH is usually negative due to the contribution of
the heat of condensation, and thus S decreases with increasing temperature
(Stannett Lal, 1962).

Generally, an increase in temperature causes an increase in the rate of

permeation of binary mixture and a decrease in selectivity. The decrease in

selectivity can be explained by the increase in agitational energy or motions of
the polymer chains at higher temperatures. According to Eyring’s hole theory,
the formation of “holes or voids ” in the polymer microstructure requires enough
energy to break down a number of secondary valence bonds. At low
temperature there are more smaller holes than larger holes within the
amorphous regions. At higher temperatures, larger holes or voids are produced
as a result of the higher agitational energy of the polymer chains (Huang and Lin,

1968).

THE NATURE OF PEMEANT

Since the ﬁrst two steps of the permeation process are (1) dissolution of -
molecules into the polymer membrane, and (2) the diffusion of the molecules
though it. Differences in either the solubility or the diffusivity can result in
separation. The solubility difference depends primarily on the difference in the
chemical nature of the permeating species. On the other hand, the diffusivity
difference is determined largely by the size and shape of these molecules and by
the degree of aggregation among the diffusing species within the polymer. For
molecules with similar shape and chemical nature, the permeation rate was
found to decrease with increasing molecular length (Huang and Lin, 1968).
Organic penetrants solubilize, swell and plasticize the polymer. The quantitative
measure of the swelling ability can be obtained by examining the solubility
parameters of the liquids and polymer. In general, solvent with the solubility

parameter (6) close to that of the polymer membrane sorbs to a greater extent

IS

than a solvent which has a value of (8) which is far from that of the polymeric.
substance (Huang and Lin, 1968). Fels (1972) explained the variability of the
permeation and separation factors with composition (other than ideal behavior)
quantitatively in the following way : “if there is a difference in swelling ability of
the two liquids towards the polymer, then one liquid will see a different polymer
structure because of the ’swelling effect of the other liquid. if the interactions of
the two liquids were the same, a constant separation factor would result, and the.
permeability would follow ideal behavior. This qualitative explanation has been
incorporated into the quantitative expression for the permeability of the individual

components in a mixture".

From the study of the permeation characteristics and the separation
behavior of 25 combinations of binary liquid mixtures through low density
polyethylene membrane, Huang and Lin (1968) found that when molecules of
similar chemical nature were compared, the permeation rate increased with
decreasing VIL, the diffusional cross section of the molecule, where V is the
molecular volume and L the maximum melecular length. From the experimental

results, they observed three general trends:

(1) For single component permeation, when comparing members of a given
homologous series of compounds, those with lower molecular weight
permeate faster than the higher molecular weight members. In binary
permeation, for a given binary mixture containing two members of a
homologous series,, the lower molecular weight member permeates

preferentially.

(2) For single component permeation, molecules with a smaller cross section
permeate faster, when comparing molecules of similar molecular weight and
chemical nature. For binary liquid permeation, molecules with smaller cross

sections will permeate at a faster rate than the other.

(3) In liquid permeation, shape and size effects predominate for molecules with
small differences in chemical nature. However, molecules with large
differences in chemical nature are not as affected by their shape and size,
but depend more on parameters such as solubility, which are related to the

chemical nature of the molecule.

DeLassus and Strandburg (1991) studied the effects of some parameters
for selected ﬂavor molecules. They investigated the diffusion coefﬁcient for two
families of perrneants at 10 to 18 Pa partial pressure, in a vinylidene chloride
copolymer ﬁlm. For both the linear esters and the n-alkanes evaluated, the
diffusion coefﬁcient decreases smoothly, as the size of the perrneant increases.
For linear molecules, the diffusion coefﬁcient changes slowly as the perrneant
changes size. For more spherical molecules, the diffusion coefﬁcient is
expected to change more rapidly (Berens and Hopfenberg, 1982). The solubility
coefﬁcient has been observed to be strongly related to the boiling point within a
family of penneants. As the boiling point increases, the solubility increase. The
act of solubilization from the vapor phase into a polymer may be analyzed as
condensation followed by mixing. 'Within a family of penneants, the heat of
condensation varies more than the heat of mixing, hence the solubility coefﬁcient

follows the boiling point closely.

I7

NATURE OF POLYMER

During the permeation process, perrneant molecules pass through
temporary voids or “holes” in the amorphous polymer regions. These voids are
the result of the temperature dependent segmental motion of the polymer chains.
The magnitude of the diffusion rate depends both on the perrneant and the
polymer. Factors which improve barrier properties of a polymer relate to the
tightness of molecular packing and forces which restrict the segmental
movement of the polymer. The regularity of branching and the number and
length of branches in polymer are recognized as important to the barrier

properties (Murray, 1985).

The existence of crystalline regions in the polymer have at least three effects on

the sorption and diffusion process :

(1) The crystalline region is essentially impermeable to perrneant molecules i.e.
sorption and diffusion occur almost exclusively through the amorphous

component. Hence, less polymeric material is available to the diffusing

species.

(2) The diffusing molecule must take a more tortuous pathway through the semi-

crystalline polymer in order to avoid the impermeable crystalline domains.

(3) The crystalline domains, acting like giant cross-linking regions, impose

strong constraints on the amorphous phase and give rise to considerable

I8

decrease in the mobility of the amorphous chain segment. Thus, the
amorphous phase in a‘semi-crystalline polymer is usually less permeable

than in a fully amorphous sample (Mark _e_t_a_il., 1985).

Any factor which tends to make the polymer - chain segments less mobile,
or pack more closely, will decrease the permeation rate. The permeation rate
can be expected to decrease as the symmetry and cohesive energy density of

the polymer increases.

The interaction of polymer and perrneant is a major consideration when
the two materials form solutions or the perrneant swells or plasticizes the
polymer, creating enhanced segmental motion and larger voids. The presence _
of a plasticzing component such as water in the binary permeating mixture
should result in permeation enhancement, i.e. 0 greater than unity. However,
Huang and Jarvis (1970) observed depression of permeation rates below the
ideal rates in a plasticized system. This was shown to be due to other
phenomena masking the initial plasticizing action of water. Several workers have
postulated that the permeation of water through polymer membrane can be
hindered by the formation of water clusters. The signiﬁcant permeation
depression observed for water-alcohol solutions through cellophane is explained
by the clustering of water molecules. The clustering of water molecules
dominates the effect of plasticization, resulting in a depression of the permeation

rate from the ideal rate.

19

Liu et al. (1988) found an increase in the diffusion of toluene vapor through
laminates containing a water - sensitive barrier layer as a function of solid water.
DeLassus et al. (1988) showed that moisture had considerable plasticizing effect
on EVOH (ethylene vinyl alcohol copolymer), resulting in increased permeability
and diffusion of an aldehyde (i.e. trans-2-hexanal). Landois-Garza and
Hotchkiss (1988) reported that the permeability and diffusion of an ester (i.e.
ethyl propionate) in PVOH (poly vinyl alcohol copolymer) decrease when the
relative humidity increased. Harzidimitriu et al. (1987) showed that for some
organic vapors, permeability through various mutilayered ﬁlms increased when

relative humidity increased.

Johansson and Leufven (1994) investigated the inﬂuence of humidity on I
the sorption, diffusion and permeation of alcohols and aldehydes in three
common packaging polymers (linear low density polyethylene, LLDPE; high
density polyethylene, HDPE; and ethylene vinyl alcohol copolymer, EVAL).
Higher humidity decreased diffusion of alcohol, and increased diffusion of
aldehyde. This might be explained by the combination of the'plasticizing effect
of water with the interaction between aroma and water vapors. Relative humidity
had a great inﬂuence on barrier properties of polyethylene ﬁlm with lower
crystallinity (i.e. LLDPE) than on more crystalline ﬁlm (i.e. HDPE). The effect of

water was more pronounced with the polar EVAL ﬁlms.

20

CONCENTRATION

The concentration (or partial pressure) of organic vapor in equilibrium with
a plastic can affect the vapors permeability constant. For perrneants with
relatively high solubility in polymers, such as organics, the concentration
dependence of D becomes important, since the organic penetrants are capable
of plasticizing the polymer chain segments, resulting in a rapid increase of D with

increasing perrneant concentration.

Studies by Zobel (1985) on permeation of limonene in polyethylene at
25°C indicated that at perrneant pressure less than about 10%of the saturated
vapor pressure, the permeability was not affected. However, at penneant
pressure above about 15 to 20% of the saturation vapor pressure, he found that
the permeability increased sharply with increasing penneant pressure. Landois-
Garza and Hotchkiss( 1988) found that the permeability of ethyl propionate
through dry polyvinyl alcohol was independent of concentration below about 30%
of the saturation vapor pressure. Above this concentration, the permeation rate

increased sharply.
PERMEANTION MEASUREMENT

ORGANIC VAPOR PERMEATION:

For permeation studies, quasi-isostatic and isostatic methods are
commonly employed for determining the diffusion of organic vapors through

barrier ﬁlms using gas chromatographic analysis for quantiﬁcation (Stannett et al,

21

1972; Zobel, 1982; Baner et al., 1986; Hernandez Lal.,1986; DeLassus, 1985).
The partial pressure difference of the test vapor provides the driving force for
permeation, with the total pressure on both sides of the ﬁlm being one

atmosphere.

In the quasi-isostatic method, the permeated gas of vapor is accumulated
in the lower concentration chamber of the permeability cell, and monitored as a
function of time. The total quantity of penetrant to have transmitted through the

ﬁlm is plotted as a function of time.

The isostatic method allows for the continuous collection of permeation
data of an organic vapor or gas through a polymer membrane from the initial
time zero to steady state conditions, as a function of temperature and perrneant
concentration. A constant concentration of perrneant vapor is continually ﬂowed
through the high concentration cell chamber. At the same time a constant ﬂow
of carrier gas is passed through the lower cell chamber, removing perrneant
vapor at a constant rate and conveying it to the detector apparatus. At pre -
selected time intervals the concentration of penetrant in the carrier system
ﬂowing through the low concentration cell chamber is determined, and the
transmission rate is monitored continually until steady state conditions are

attained.

MATERIALS AND METHODS

BLISTER TRAYS AND FILM SAMPLES

Blister trays (L X W X D - 2.75” X 1.5” X 0.25” and ﬂange width of 1/4”) as
shown in Figure 1, were therrnoforrned from a Barex-polyethylene coextrusion
and ﬁlm samples of three different ethylene-vinyl acetate copolymers (ﬁlm A-5.5
mil, 93.5% ethylene/ 6.5% vinyl acetate) (ﬁlm B-5 mil, 91% ethylene! 9% vinyl
acetate) (ﬁlm C-5 mil, 88% ethylene! 12% vinyl acetate) were provided by the
Dial Corp.(Scottsdale, AZ), and were used in all studies. Barex is a copolymer of
74% acrylonitrile and 26% methyl acrylate modiﬁed with a butadiene rubber
I graft. The ﬁlm samples serve as the membrane lid for the fragrance delivery

system and were heat sealed to the tray.

FRAGRANCE FORMULATIONS

The fragrance formulations evaluated in the study were provided by the
Dial Corp, and were a ﬂoral type. The nine different formulations evaluated were
formulated with 3 different levels of Cabosil and 3 lsopar content levels, as
indicated below: Cabosil was used as a thickening agent, and lsopar served as
the dispersing solvent. The make up of the respective test formulations are

summarized in Table 1.

22

23

/— Semi-permeable Lid Membrane

 

   

 

L Fragrance Formulation

   

BAREX! LDPE Laminate Tray

Figure 1. Fragrance delivery system

24

Table 1. Fragrance formulations

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Formulation lsopar Content (wt %) Cabosil Content (wt %)
1 2 4
2 2 6
3 2 8
4 5 4
5 5 6
6 5 8
7 8 4
8 8 6
9 8 8
PROBE COMPOUNDS

To provide a relative evaluation of the aroma barrier properties of the
polymer ﬁlm, four probe compounds, characteristic of the fragrance proﬁle, were
selected. The probe compounds were selected based on their relative
concentration in the aroma proﬁle, contribution to the aroma, low sensory
threshold, and ease of analysis. The probe compounds selected included
linalool, phenethyl alcohol, benzyl acetate, anda-hexyl cinnamaldehyde and were

obtained from Aldrich Chemicals (Milwaukee, WI).

Linaiool

0H

Molecular weight
Boiling point
Refractive index

Density

phenethyl alcohol

CHZCHZOH

Molecular weight
Boiling point
Melting point
Refractive index

Density

154.25
1 94-1 97°” 20 mm
1.462

0.87

122.17 f
219-221°/750 mm
-27°

1.532

1.023

26

benzyl acetate

CHZOCOCHEI

Molecular weight 150.18
Boiling point 206°
Melting point -51°
Refractive index 1.502

Density 1 .04

or-hexyl cinnamaldehyde

\ CHO
Molecular weight 216.33
Boiling point 174-176°/15 mm

Refractive index 1.55

Density 0.95

27

METHANOL ABSOLUTE (Baker analyzed - J.T. Baker lnc., philipsburg, NJ)
Molecular weight 32.04
Methanol was used as the solvent for preparing standard solutions of the
probe compounds for calibration, and to quantify the levels of the respective

probe compounds in the fragrance formulations.

NITROGEN - CARRIER GAS
High purity dry nitrogen (99.98%) provided by the AGA Gas Inc

(Cleveland, OH) was used as the carrier gas.

ANDEX LABORATORY BLISTER SEALER

The blister trays were mounted on a wooden mold, and ﬁlled with 3 ml of
test fragrance formulation. A sample of the ethylene-vinyl acetate (EVA)
copolymer ﬁlm was cut to the size of the blister, placed over the blister, covered
with Teﬂon ﬁlm and heat sealed. An effective heat seal was obtained at a
temperature 280°F and dwell time of 15 sec for ﬁlm A and 285°F and dwell time
of 10 sec for ﬁlm 8 and ﬁlm C. The heat seal obtained was examined visually
and tested manually for peel resistance. The sealing conditions were based on
the endotherrn proﬁles of the three ﬁlms by differential scanning calorimetry
(DSC) analysis At this seal temperature, the ﬁlm samples exhibiting the lowest
onset temperature and melting point required the shortest dwell time to obtain an

effective heat seal.

28

ANALYTICAL

A Hewlett Packard Model 5890A gas chromatography (GC), equipped
with 30m X 0.32mm ID SPB-5 nonpolar capillary column having a 25pm ﬁlm of
5%diphenyl, 94%dimethyl, and 1% vinyl polysiloxane phases obtained from
Supelco (Bellefonte, PA), and ﬂame ionization detector was used for all
analyses. The GC was interfaced to a HP 3392A integrator to record all data.

The GC was operated in the splitless mode with the following conditions.

Initial temperature - 60°C, initial time - 1.00 min, Final temperature - 260°C, Final
time - 10.00 min, Rate - 4°Clmin, Purge off - 1.00 min, Range - 4, Attenuation -
2, Total run time - 61 min, Inlet temperature - 220°C, Detector temperature -
220°C.

The four probe compounds were eluted at the following retention times: linalool -
10.72 min, phenethyl alcohol - 11.06 min, benzyl acetate - 12.82 min, a-hexyl
cinnamaldehyde - 31.51 min.

Standard calibration curves of area response versus mass of probe
compound, were constructed for each probe compound, from standard solutions
of known concentration. Standard solutions were prepared by dissolution of
known quantities of linalool, phenethyl alcohol, benzyl acetate, and a-hexyl
cinnamaldehyde in methanol, respectively. The concentration of the probe

compounds in each study was determined by reference to the calibration curves.

29‘

PERMEATION MEASUREMENTS

Permeability experiments were carried out at 50°C for a period of thirty
days at a ﬂow rate of 20 cclmin. The permeability cells used in this study are
described by Hernandez et al. (1986). The test apparatus is of our own design,
and was used to monitor the transport of volatile fragrance compounds through
the ﬁlled delivery tray system by the isostatic method of measurement. The cells
are comprised of two aluminum disc shaped plates and a center ring, that when
clamped together to form the complete cell which was comprised of an upper
chamber, a lower chamber, and a middle chamber. Each cell chamber contains
and inlet and outlet port for the continuous ﬂow of a carrier gas stream. Analysis
of penetrant concentration was based on a chromatographic procedure, with
ﬂame ionization detection (FID).

A schematic diagram of the system utilized is presented in Figure 2. All
permeation cells and cell parts were rinsed with acetone and baked at 120°C for
a period of at least 72 hours to remove any residual sorbed perrneant from the
previous experiment. The “0” rings in the permeation cells were replaced before
each run. Hermetic isolation of the cell chamber from the environment is
achieved by the compression of a Viton “O” ring between the lower chamber and
the center ring. VitonTM is a ﬂuorocarbon elastomer compound which is resistant
to attack and swelling by most organic vapors.

A Blue M electric StabiI-therm Mechanical convection oven with Protronics
ll control (Fisher Scientiﬁc Co., USA) was used in the study to provide a constant

temperature environment for mass transport studies. Protronics II control

30

consists of a main temperature control and over temperature alarm (OTA)
control. When the main control set point was 50°C, the OTA set point was 60°C.
10°C above the desired operating temperature of the oven, as veriﬁed with a
thermometer.

For each permeation test cell, a sealed fragrance delivery tray was
placed in the lower chamber, and the upper cell chamber was covered with
aluminum foil to reduce the cell volume. Carrier gas was then ﬂowed through the
middle chamber. The inlet an outlet ports of the lower and upper cell chambers
were closed. In operation, the assembled cells (two) were placed horizontally on
the top rack of the oven and were connected to the sampling cells. The
sampling cell also has three chambers with the center one being isolated from .
the top and bottom cell chamber by aluminum foil. The center chamber contains
a sampling port from which aliquots are taken for quantiﬁcation of perrneant
concentration. Rotameters were used to provide a ﬁxed and constant gas ﬂow
through the test and sampling cells. The carrier gas ﬂow to the rotameter were
regulated by Nupro “M” series needle valves. Electronic mass ﬂow meters
manufactured by Sierra Instruments (Monterey,CA), Top Trak 820 model, 9-20
SCCM with an accuracy of 2% of full scale and 0.5% repeatability were
incorporated between the rotameter and the testing cell to provide a continuous

indication that a constant rate of ﬂow of carrier

31

 

   
 
 
  
  

Needle Valve p 4

Flow Meter

   

Mass Flow Meter Mass Flow Meter

 

 

 

 

 

 

 

 

emﬂratgre Controlled Chamber
Test Sampling Sampling Test
Cell 1 Cell 1 Cell 2 Cell 2
Fragrance Sampling Sampling Fragrance
DeiiVery Tray P0" P0" Delivery Tray

 

 

\

Figure 2. Schematic of fragrance delivery system permeation test apparatus.

32

gas was maintained. The mass ﬂow meter reading was also veriﬁed using a
bubble ﬂow meter. All connections were made with copper refrigeration tubing
1/8” OD and 1.65 mm ID. All ﬁttings and tubing connections used were
Swagelok ﬁttings. Before each run, the test cell and sampling cells were ﬂushed
with nitrogen and an aliquot was taken from the sampling cell and injected
directly into the GC to determine the presence of residual organic vapors.

At predetermined time intervals (every 72 hours) a 50 microliter sample
was removed from the middle chamber of the sampling cell with a gas tight
syringe(1750$N, 500pl, Hamilton) and injected directly into the gas
chromatograph. Replicated samples were analyzed and the average values
reported.

The transmission rate or ﬂux of the probe compounds through the
fragrance delivery system was calculated by substitution into the following
equaﬁon:

min

Fqu(—g-) = AU x CF x(——1;-—.-)x ﬂow rate x 1440(—)
day V in] day

(19)
where AU = average area units from gas chromatogram

CF = calibration factor (g/AU)

Vrnj = sample injection volume (0.05 cc)

Flow rate = cell ﬂow rate (20 cclmin)

The sensitivity of the GC was determined with a calibration standard, prior

to all sample analysis.

33

MASS BALANCE STUDIES

The concentration of probe compounds in the formulation was determined
by chromatographic analysis prior to and following termination of the permeation
experiments, and a mass balance determination was made for each probe
compound. The blister trays were also weighed before and after the permeability
experiment to determined global loss , where global loss is deﬁned as the total
level of volatiles lost.

Global loss (%) = "“t'a' Wt ' “"5" M x 100 (20)

initial wt

 

The initial concentration of the probe compounds in the fragrance
formulation was determined before each run by dissolving 0.1 ml of the
fragrance formulation in methanol, in a 200 ml volumetric ﬂask. 0.5uL aliquot of
this sample was injected into the GC for analysis. All analyses was done in
duplicate and the average area response used to calculate the initial
concentration of the probes in the fragrance formulation. After the permeation
experiments were completed, a known amount (<0.05 9) of the fragrance
formulation remaining, was weighed into a 100 ml volumetric ﬂask partially ﬁlled
with solvent. The solution is swirled to dissolve the fragrance formulation and
made-up to volume with methanol. A 0.5pL aliquot of this sample was analyzed
by GC to determine the ﬁnal concentration of probes. From the difference
between the quantity of probe compounds before and after completion of the

permeability experiments, the percent loss of individual probes was determined.

34

 

initial quantitty - ﬁnal quantity x100

. . . ' (21)
IDIIIaI quantity

% probe loss =

35

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

m o v N o v m o v 2828 .880
N m m m. m m N N N 29:8 :88.
NF N: Na N. Na N. N. NF NF 22:8 9882 .25
NN 8N N «N N NN _N 8 3 «mass: 39:53
N o v m o v N m e .828 .288
m m m m m. m. N N N 2828 :88.
m m m a m a m m a 29:8 9282 .25
S t 2 8 3 2 NF 3 2 «mass: m..m<_¢<>
. m o v a o e o m .V 22:8 .288
N m m m m. m N N N 2828 :88.
m8 me no no we 3 no no 3 29:8 238: .25
m m N m m .V m N a «wuss: m..m<.¢<>
«mass: 2::
.625 m2: “.o 2053 .N 023

 

36

STATISTICAL ANALYSIS

The statistical design, as shown in Table 2 was based on a three(3) level,
three (3) variable factorial design and considered three variables including:
ethylene-vinyl acetate copolymer composition, isopar content, and cabosil
content. For each variable, three concentration levels were selected in order to
create a linear level of concentration that could be easily extrapolated after
experimental analysis.

For statistical analysis, the slopes obtained from transmission proﬁle curves of
each probe compound were utilized. The slope of the transmission proﬁle
curves were used as an indication of the barrier characteristics of each system
considered. .

The analysis of variance (ANOVA) statistical technique was then used to
examine the variability of the individual observations within each group, as well
as the variability between group means. This analysis allowed determination of
the variables which had the most signiﬁcant effect on the permeability of
fragrance volatiles from the fragrance delivery system. A Simple Factorial and a
One-way ANOVA in SPSS for Windows was used to perform this statistical
analysis.

The following assumptions were made when performing the analysis of
variance:

. sample data/observation is an independent random sample from a normal
population.

0 homogeneous within group variance across all groups.

37

The statistical procedure for comparing two or more treatment means,
involves testing of the null hypothesis of no effect. If the analysis leads to the
conclusion that we could expect such mean differences quite frequently by
chance, we do not reject the null hypothesis and conclude that we have no good
evidence of a real treatment effect. If the analysis indicates that the observed
differences would rarely occur in random samples drawn from populations with
equal means and variances, we reject the null hypothesis and conclude that at
least one treatment had a real effect. At least one of the means is said to be
signiﬁcantly different from the others. If the probability of the statistical analysis
is less than 5% of the variation among means, the null hypothesis is rejected and
we can say that the means are signiﬁcantly different.

The Simple Factorial ANOVA procedure considers the probability of the null
hypothesis, that the data are a sample from a population in which the mean of a
test variable is equal in several groups of cases deﬁned by factor variables. It
differs from One-way ANOVA in handling several grouping variables

simultaneously.

RESULT AND DISCUSSION

VAPOR PRESSURE AND VAPOR ACTIVITY OF THE FRAGRANCE
FORMULATION:

The saturation vapor pressure, vapor pressure and vapor activity of the
individual probe compounds in the test fragrance formulations are summarized in
Tables 3-5, respectively. The vapor pressure and vapor activity values of the
probe compounds in the fragrance formulations were found to be higher with an
increase in lsopar content. The saturation vapor pressure of hexyl
cinnamaldehyde was lower than the other probe compounds, which could be
explained by its very high boiling point (174°C). The vapor pressure of hexyl
cinnamaldehyde in the fragrance formulations was not detected.

The concentration of the respective probe compounds in the test
fragrance formulations are tabulated in Table 6. The tabulated data shows
linalool to be present at the highest concentration in all the fragrance
formulations, as compared to the other selected fragrance volatiles. This in part,
also explains the higher vapor pressure levels of linalool in the fragrance

formulations.

38

39

Table 3. SATURATION VAPOR PRESSURE OF PROBE COMPOUNDS AT

 

 

 

 

50°C (mmHg)
Linaiool Phenethyl Alcohol Benzyl Acetate a—Hexyl Cinnamaldehyde
0.6905 0.1128 0.3359 0.0014

 

 

 

 

FORMULATIONS AT 50°C (mmHg)

Table _4. VAPOR PRESSURE OF PROBES IN THE FRAGRANCE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Linaiool Phenethyl Benzyl a—Hexyl
Formulations Alcohol Acetate Cinnamaldehyde
1 0.1983 0.0685 0.0823 0
2 0.1841 0.0666 0.0815 0
3 0.1409 , 0.0508 0.0625 0
4 0.2160 0.0776 0.0821 0
5 0.2519 0.0881 0.1019 0
6 0.2184 0.0850 0.0916 0
7 0.2595 0.0967 0.0865 0
8 0.2840 0.1097 0.1051 0
9 0.2582 0.0951 0.0839 0

 

 

40

Table 5. VAPOR ACTIVITY OF PROBES IN FRAGRACNE FORMULATIONS

 

 

 

 

 

 

 

 

 

 

 

Fragrance Linaiool Phenethyl Benzyl a-Hexyl
Formulations Alcohol Acetate Cinnamaldehyde
1 0.2871 0.6071 0.2451 0
2 0.2667 0.5903 0.2427 0
3 0.2040 0.4507 0.1861 0
4 0.3129 0.6884 0.2444 0
5 0.3648 0.7812 0.3034 0
6 0.3162 0.7534 0.2727 0
7 0.3758 0.8575 0.2574 0
8 0.4114 0.9729 0.3128 0
9 0.3739 0.8432 0.2498 0

 

 

 

 

 

 

Table 6. THE CONCENTRATION OF THE PROBE COMPOUNDS(g/ml) IN THE

41

 

 

 

 

 

 

 

 

 

 

 

FRAGRANCE FORMULATIONS
Fragrance Linaiool Phenethyl Benzyl a—Hexyl
F orrnulations Alcohol Acetate Cinnamaldehyde
1 0.1968 0.1471 0.0736 0.0007
2 0.1983 7 0.1456 0.0753 0.0007
3 0.2204 0.1597 0.0821 0.0009
4 0.2344 0.1753 0.0888 0.0005
5 0.2042 0.1521 0.0787 0.0004
6 0.2044 0.1521 0.0785 0.0005
7 0.2375 0.1656 0.0877 0.0006
8 0.2084 0.1512 0.0800 0.0007
9 0.1949 0.1407 0.0740 0.0009

 

 

 

 

 

 

42

THE PERMEATION STUDIES OF FRAGRANCE VOLATILES

The permeability studies were carried out at 50°C at a cell ﬂow rate of
20cclmin for all fragrance formulations. Studies were terminated after 30 days of
continuously monitoring the transmission rate of each probe compound through
the fragrance delivery system membrane. The obtained mass ﬂow values were
assumed to be diffusion controlled, which simulated the conditions for the loss of
fragrance volatiles for the fragrance delivery system under end-use applications.
At the actual end-use application, the external membrane of the fragrance
delivery system is exposed to an inﬁnite volume into which the fragrance volatiles
would diffuse.

Three distinct steps are involved in the transport of organic compounds
through a polymeric ﬁlm ;

(1) absorption of perrneant molecules at the polymer ﬁlm surface

(2) diffusion of the perrneant molecules through the polymer bulk phase

(3) removal of the perrneant molecules from the low concentration ﬁlm surface by
evaporation.

The total or global loss and the percent loss of the four probe compounds
through ﬁlm A, ﬁlm B, and ﬁlm C, on a weight percent basis, are summarized in
Tables 7-10 respectively. As shown, after 4 weeks of test, nearly quantitative
losses of linalool, phenethyl alcohol, and benzy acetate were found, while about
50% loss of a—hexyl cinnamaldehyde was observed at the test conditions of 50°C

and a carrier gas velocity of 20cclmin.

Table 7. GLOBAL LOSS OR THE TOTAL VOLATILES LOSS FROM

FRAGRACNE FORMULATIONS THROUGH FILM A, FILM B, AND FILM C

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Percent Loss
Formulations

Film A Film 8 Film C
1 45.43 43.34 44.85
2 43.77 46.05 44.62
3 43.26 45.07 41.04
4 47.18 43.87 44.33
5 42.72 43.82 45.19
6 39.91 43.86 45.27
7 45.69 50.23 46.61
8 46.07 45.44 46.07
9 44.33 43.88 44.69

 

 

 

 

 

44

Table 8. PERCENT LOSS OF SPECIFIC PROBE COMPOUNDS FROM

FRAGRANCE FORMULATION THROUGH FILM A.

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Percent loss (wt/wt %)
formulation
Linaiool Phenethyl Benzyl a-hexyl
alcohol acetate cinnamaldehyde

1 96.95 83.55 92.34 57.51
2 97.36 82.68 99.40 38.30
3 98.86 84.06 99.69 70.66
4 98.72 86.68 99.56 44.81
5 ' 97.46 80.31 98.83 30.41
6 96.88 77.00 98.75 N/A
7 97.24 84.93 98.93 64.85
8 97.65 84.38 99.15 75.28
9 97.61 83.12 98.82 72.34

 

 

 

 

 

NIA denotes not available

 

45

Table 9. PERCENT LOSS OF SPECIFIC PROBE COMPOUNDS FROM

FRAGRANCE FORMULATION THROUGH FILM B.

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Percent loss (wt/wt %)
formulation
Linaiool Phenethyl Benzyl a-hexyl
alcohol acetate cinnamaldehyde

1 97.52 77.74 98.27 35.30
2 98.68 80.51 99.41 43.76
3 99.25 83.43 99.32 59.12
4 98.06 78.44 98.98 26.54
5 97.99 75.64 99.13 NIA
6 98.06 80.05 99.54 N/A
7 99.27 93.06 100 63.83
8 98.05 85.24 99.53 54.89
9 97.52 83.09 99.37 64.88

 

 

 

 

 

NIA denotes not available

 

46

Table 10. PERCENT LOSS OF SPECIFIC PROBE COMPOUNDS FROM

FRAGRANCE FORMULATION THROUGH FILM C.

 

 

 

 

 

 

 

 

 

 

 

 

Fragrance Percent loss (wt/wt %)
formulation
Linaiool Phenethyl Benzyl a-hexyl
alcohol acetate cinnamaldehyde

1 99.46 87.77 99.74 64.37
2 99.62 87.65 100 42.90
3 99.45 85.74 100 56.11
4 99.56 90.71 100 57.76
5 99.56 87.33 100 NIA
6 100 89.94 . 100 32.54
7 99.68 92.71 100 68.90
8 99.59 90.99 100 75.81
9 99.49 90.04 100 33.76

 

 

 

 

 

NIA denotes not available

 

47

The respective transmission proﬁle curves for linalool, phenethyl alcohol
and benzyl acetate, from fragrance formulations 1-9, through ﬁlm A, ﬁlm B. and
ﬁlm C are presented in Figures 3-83, where the ﬂux of the speciﬁc permeating
fragrance volatiles (glday) is plotted as a function of run time. The level of 01-
hexyl cinnamaldehyde was below the limit of detectability by chromatography
analysis. Therefore, no permeation behavior for this probe volatile was obtained.
The reported data are the average of duplicate values. The ﬂux data or
transmission rate values through ﬁlm A, ﬁlm 8, and ﬁlm C for the respective
probe compounds, at 50°C and ﬂow rate of 20cclmin, are summarized in Tables
15-41, and are presented in Appendix C.

From the transmission proﬁle data, linalool shows the highest transmission rate
when compared to phenethyl alcohol, benzyl acetate, and a—hexyl
cinnamaldehyde. Linaiool is present in the highest concentration in the
fragrance formulation and has the highest vapor pressure value, which explains
the observed higher transmission rate of linalool. Also, a—hexyl cinnamaldehyde
was not detected in the permeated vapor stream in the present studies, which
can be attributed to its low concentration in the fragrance formulation and high
boiling point (i.e. low vapor pressure).

If a polymer ﬁlm is placed in contact with an inﬁnite concentration of
diffusant, the transmission curve would follow Fickian behavior and show an
initial induction period followed by a non-steady state transmission rate of

diffusion, which precedes a steady state rate. However, for the fragrance

48

delivery system studied, there is a limited concentration of fragrance volatiles in
the system, so there will be a continuous decrease in fragrance volatiles
concentration, as well as a continuous decrease in the partial pressure gradient
with time, as a result of fragrance volatiles diffusion. These dynamic factors and
the limited fragrance volatile concentration levels present in the delivery system
trays will result in the transmission rate proﬁle curves observed for the respective
penetrant/delivery system membranes investigated.

As shown in transmission proﬁle curves (see Figures 7 to 87) , the permeability
behavior of the respective penetrant/barrier membrane systems studied, typically
followed a Gaussian type plot, where there was an initial rapid rate of increase in
the penetrant ﬂux to a maximum level, which was then followed by a linear
decrease in the rate of diffusion with time. The ﬁnite concentration of fragrance
volatile in the fragrance formulations and the dynamic nature of the system,
which resulted in a continuous change in both the penetrant driving force
concentration and composition of the fragrance copolymer, are both contributing
factors to the Gaussian-like transmission rate proﬁle curves obtained. While the
transmission rate proﬁle curves obtained for linalool and benzyl acetate followed
Gaussian-like behavior, the plotted ﬂux data obtained for phenethyl alcohol
showed a signiﬁcant degree of data scattering (for example see Figures 4, 7, 10
and 31 ). Although the permeability behavior of phenethyl alcohol showed
considerable data scattering, it was assumed that a smooth curve ﬁt of the ﬂux
data would follow the expected rapid increase in the penetrant ﬂux to maximum,

preceded by a steady decline in the ﬂux with time. The observed scatter of the

49

data about a smooth ﬁt curve can result from errors arising from the gas
chromatographic analysis of phenethyl alcohol level in the carrier gas stream.

Since the mass transfer rates are determined by substitution into Equation (22),

l .
Flux = A.U x or x T x ﬂow rate x 1440(93) (22)
Vm] day

it follows that an inaccurate value of detector response (AU) would result in
either an overestimation or an underestimation of the ﬂux rate of phenethyl
alcohol. In this regard, it is important to note that gas chromatographic analysis
is valid only in a negative sense in that a response from the detector, under
speciﬁed conditions, is recorded. Since it is possible for different compounds to
have identical, or very similar retention times, poor peak resolution of a co-
perrneant can result in a detector response value (A.U) for phenethyl alcohol,
which would overestimate its actual concentration level and its concomitant ﬂux
rate.

The permeation process involves dissolution of molecules into the
polymer membrane and diffusion of the molecules through the membrane.
Differences in either the solubility or diffusivity can effect the transmission
characteristics of the fragrance volatiles. The solubility difference depends on
the difference in the chemical nature of the permeating species. However, the
difference in diffusivity is primarily determined by the size and shape of the
molecules, and by the degree of aggregation among the diffusing species in the
polymer. In general, polar compounds permeate polar membranes faster than
non-polar compounds. Therefore, linalool and phenethyl alcohol, which are

more polar, as compared to benzyl acetate and a-hexyl cinnamaldehyde, would

50

1.6

 

1.41»

1.2 «>

03 .. T-o: ‘FIIEEJdéyI

 

0.6 w

Flux (glday) x E-2

0.4 ..

0.2 1

 

 

 

O (,7 + A. . * : *
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 3. Transmission proﬁle of linalool through a ﬁlm A from
fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

0.7

 

0.6 ll ~~~~~~~~~~
0.5 «I
0.4 I-
0.3 l

0.2 ..

Flux (glday) x E-Z

0.1 «-

 

 

o 4, ‘ ~ . . : - 2 t T
0 72 144 218 288 380 432 504 578 648 720
Run time (houre)

 

Figure 4. Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

SI

1.2

 

 

I i
i -o— Flux(glday) I

 

0.8 ..

0.6 i-

0.4 1)

Flux (glday) x E-2

0.2-<-

 

 

09 , + : : - - ‘, .ﬁ
0 72 144 218 288 380 432 504 578 848 720

Run time (houre)

Figure 5. Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

 

 

l

[ -<>-— Flux(glday)ﬁf

 

Flux (glday) x E-Z

 

l

 

0 v '. : % -. : s r ;
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 6. Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #2 at 50°C and ﬂow rate of 20cdmin

52

0.6

 

0.7 ~

 

{ -o— Flux(gldayL

 

0.6 w

0.5 l

Flux (glday) x E-2

 

 

O 4, t + *ﬁ : ‘ % - *2 4
0 72 144 216 288 360 432 504 576 648 720
Run time (hours)

 

 

Figure 7.Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

 

 

i-°- Flam/dam

 

Flux (glday) x E-2

 

 

 

O 2 : : 2 . : : : .
0 72 144 216 288 360 432 504 576 648 720

’7—

Run time (hours)

Figure 8. Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

53

 

 

, -<>— F lux(glday)_i

 

Flux (glday) X E-2

 

 

 

0 , ‘ . * : k * t .
0 72 144‘ 216 288 380 432 504 578 848 720
Run time (hours)

Figure 9. Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

 

 

__

L—o— Fqu(g/day) l

 

Flux (glday) X E-2

 

 

0 .

 

 

0 72 144 216 266 360 432 504 578 848 720
Run time (hours)

Figure 10. Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

54

1.4

 

1.21-

d
J
I

 

I -<>— Flam/day);

 

0.6 <

Flux (glday) X E-2

 

 

 

ﬂ

0 72 144 218 288 360 432 504 578 648 720
Run time (hours)

Figure 11. Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

 

 

[-0— Fiux(gldeyTJ

 

Flux (glday) X E-Z

 

 

 

O f : .2 * : - . .
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

‘1

Figure 12. Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin

55

 

 

: —<>— Fluxg/day) .

 

Flux (glday) X E-2

 

 

 

L A A A L A. A
f

f

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 13. Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin

1.4

 

 

l -o— Fiux(glday) 7

 

Flux (glday) x 2.2

 

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 14. Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance fonnuiation #4 at 50°C and ﬂow rate of 20cclmin

56

 

 

l —<>— Flux(glday) ;

 

Flux (glday) x 2.2

 

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 15. Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin

 

.0
o:

)

l-o-Fluxialdﬁl

b

Flux (glday) X E-2
a O 0

.°
N

 

 

0.1
O r t : . * + i t :
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

 

Figure 16. Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #5 at 50°C and ﬂow rate of 2066/min

57

 

 

-o— Flux(glday)I

 

Flux (glday) X E-2

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 17. Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin

 

.N
tn

N

[-0— ’ ""Fuxiélliixl,

 

   

Flux (glday) X E-2
.. 3‘.

0.5 1-

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 18. Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

58

_e
N

 

d
J
v

9
o

 

weave?»
>

 

Flux (glday) X E-2
p o
b O

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 19.Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

 

 

t0- FlungldeyT]

.0
o:

 

Flux (glday) x 2.2

.9
;

 

 

 

O 4 : 4 - v : t + : .
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 20.Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

In

Fig
ffor

59

3.5

 

Flux (glday) X E-2

 

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 21 .Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

1.2

 

 

I —o— Fiux(glday)I

I
L

.0
o:

l
J

Flux (glday) X E-2
O
O

 

 

 

0 v . - - 1 . . : +
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 22.Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

60

 

   

 

L-°-._f_'_°§$g’93!8

G
A
v

Flux (glday) X E-2
g .0

.°
A

 

0.2

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 23.Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

3.5

 

   
 
  
  

(a!

I“
an

 

N

bO-Fluxm’devl l

Flux (glday) X E-Z
4 0|

 

 

0 sf : : ‘ * L. ; 4 s 4 1
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 24.Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #8 at 50°C and ﬂew rate of 20cclmin

 

6I

 

..———. -._.—__.

T —<>— Flux(glday);

 

Flux (glday) x 2-2
’53 3

 

 

O 2 ‘f : t 4 2 :F % :
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 25. Transmission proﬁle of phenethyl alcohol through a ﬁlm A
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

 

 

 

 

 

 

 

1.8
N
d. [:0— Flux(g/day)]
X
‘5‘.
3
E
x
2
IL
0-v : ‘ : * + 2 t : : 1
0 72144218288360432504578848720

Run time (hours)

Figure 26.Transmission proﬁle of benayl acetate through a ﬁlm A
from fragrance formulation #8 at 50°C and flow rate of 20cclmin

62

 

 
  

 

2.5 .. bo—meday)?

Flux (glday) x 2.2
0'

 

 

0 72 144 218 288 380 432 504’ 578 848 720
Run time (hours)

Figure 27.Transmission proﬁle of linalool through a ﬁlm A
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

 

  

 

{-0— Fiux(glday)1:

 

Flux (glday) X E-2

 

O .2
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

 

Figure 28.Transmission proﬁle of phhenethyl alcohol through a ﬁlm A
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

Fig

63

 

Fo- Fiux(g/da—y)°

 

Flux (glday) X E-2

 

 

 

0 72 144 218 288 380 432 504 578 648 720
Run time (hours)

Figure 29.Transmission proﬁle of benzyl acetate through a ﬁlm A
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

 

7+“ ' area/«'91:

 

Flux (glday) X E-Z

 

 

 

0 72144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 30.Transmission proﬁle of linalool through a ﬁlm 8
from fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

.5
N

 

A
L
Y

 

bo- FquIo/day) ,.

Flux (glday) X E-2
9 .c .o
& o: o:

.0
Io

 

 

ol.

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 31.Transmission proﬁle of phenethyl alcohol through a ﬁlm B
from fragrance formulation #1 at 50°C and ﬂow rate of ZOcCImin

 

Z-S—T’FIGxIrI—I‘diﬁhi

 

.0

Flux (glday) X E-2
9

.°

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 32.Transmission proﬁle of benzyl acetate through a ﬁlm B
from fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

65

 

 

I -o— Hung/day)?

 

Flux (glday) X E-2

 

 

 

O * . T .
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 33.Transmission proﬁle of linalool through a ﬁlm B
from fragrance forrnuiation #2 at 50°C and ﬂow rate of 20cclmin

1.2

 

      
  

 

9
a

[ -o— Fqu(gIday)I

 

.0
o:

Flux (glday) X E-2
p
b

 

 

A L ;

ﬁﬁ

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 34.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #2 at 50°C and flow rate of 20cclmin

66

 

 

13161593932

Flux (glday) X E-2

 

 

 

0 ¥ 4. —t i T i 1 % w
0 72 144 218 288 360 432 504 578 848
Run time (hours)

Figure 35.Transmission proﬁle of benzyl acetate through a ﬁlm B
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

2.5

 

 

v

[-0- Flux(glday) J3

 

Flux (glday) x 2.2

 

 

 

 

0 72144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 36.Transmission proﬁle of linalool through a ﬁlm 8
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

67

.“
N

 

d
V

  

.0
or

._-<>-FIB"x(97¢3§I'}

Flux (glday) X E-2
O
G

.0
;

 

 

J.
T

0 72144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 37.Transmission proﬁle of phenethyl alcohol through a ﬁlm B
from fragrance forrnuiation #3 at 50°C and ﬂow rate of 20cclmin

1.4

 

 

L-o— Fluxwaayll

Flux (glday) X E-2

 

 

 

o - . - . : a
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

77

Figure 38.Transmission proﬁle of benzyl acetat through a ﬁlm B
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

68

 

 

I --o— Fiux(glday) l

 

Flux (glday) X E-2

 

 

 

0 v— . : - : ; : : .
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 39.Transmission proﬁle of linalool through a ﬁlm B
from fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin

1.2

 

.0
o:

)

-——-.-—'

E0- “989797.112

.0
as

Flux (glday) X E-2
O
a.

 

 

o A x A A J. A A

 

f

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 40.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #4 at 50°C and ﬂow rate of 20¢clmin

69

 

Fo—h “Find/659);

 

Flux (glday) X E-2
.0 .0

 

 

 

%

0 v t t t t % ; ; ,A .
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 41 .Transmission proﬁle of benzyl acetate through a ﬁlm B
from fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin

 

 

Ltﬂgxlgidax)-

Flux (glday) X E-2

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 42.Transmission proﬁle of linalool through a ﬁlm 8
from fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin

70

1.2

 

9
or

___._._‘.. _...... .—

5 —o; Hung/dag?

.0
o:

l

Flux (glday) X E-2

 

 

 

0c- 2 2*362
'0 72144216288360432504578848720

Run time (hours)

 

Figure 43.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #5 at 50°C and ﬂow rate of 200CImin

 

 

    
  

L—o— Flux(glday) I

 

A.

Flux (glday) X E-Z
c
on

 

 

0 -v - . - : .2 : : : A.
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 44.Transmission proﬁle of benzyl acetate through a ﬁlm 8
from fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin

7|

 

 

mm:

Flux (glday) X E-2

 

 

 

0 L . ' t 4 ¢ : t i .
0 723144 218 266 380 432 504 578 646 720
Run time (hours)

Figure 45.Transmission proﬁle of linalool through a ﬁlm 8
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

 

1.4

d

e

N
A
V

d
A
'

 

‘3‘

m F-w
i 0.8 '°" Fm‘ii’dt‘lﬂl
5

8

a, 0.8 4»

K

a

I 0.4

 

 

 

0 v : a r : ‘ +1 : : s
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 46.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

72

2.5

 

L—o— FIGMtIItIér—YTI

 

Flux (glday) X E-2

 

 

 

 

0 72144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 47.Transmissi0n proﬁle of benzyl acetate through a ﬁlm 8
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

 

 

 

 

 

 

 

‘2‘
III
x
3‘.
8
3 [-0— Flux(glday) :
x .
2
a.
UV . - . - : - ' 4 .
0 72 144 218 288 380 432 504 578 848 720

Run time ((hours)

Figure 48.Transmission proﬁle of linalool through a ﬁlm B
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

73

 

    

A.

.0
c

.0
a

 

l l_-°-_f'1§t9.’d_az);

Flux (glday) x 2.2

.0
;

 

.0
N

  

 

 

O

a A 1 1 A
V V

0 72144 216 288 380 432 504 578 848 720
Run time (hours)

Figure 49.Transmission proﬁle of phenethyl alcohol through a ﬁlm B
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

2.5

 

 

L—o—Huxroldayﬂ

 

Flux (glday) X E-2

 

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 50.Transmission proﬁle of benzyl acetate through a ﬁlm B
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

74

 

Ear-_- “617-16661

 

Flux (glday) x 2.2

 

 

 

0t: % ; - : . t 2 4
O 72 144 216 288 360 432 504 576 648 720

Run time (hours)

 

Figure 51 .Transmission proﬁle of linalool through a ﬁlm B
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

 

.0
or

 

P
o»

I Ko—Fqum/day)‘;

 

Flux (glday) X E-2

P
A

 

 

 

0 v 5 f t r ; % ,2 ¢ ;
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 52.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

75

 

_-—————

Eo— HMS/357)]

Flux (glday) X E-2

 

 

 

 

o V - t f v
0 72 144 218 288 380 432 504 578 648 720
Run time (hours)

Figure 53.Transmission proﬁle of benzyl acetate through a ﬁlm B
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

 

 

I -O— Flux(glday) l

 

Flux (glday) X E-2

 

 

 

A_

0v 1 4

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 54.Transmission proﬁle of linalool through a ﬁlm 8
from fragrance formulation #9 at 50°C and ﬂow rate of 20%/min

76

_A
5

 

_-
N

A
A
v

.0
a:

 

L—g— Flux(gldey) l

Flux (glday) X E-2
a: a

 

 

 

0 A. s ‘ ‘ f ‘ 4 4 t
0 72 144 216 288 360 432 504 578 848 720
Run time (hours)

 

Figure 55.Transmission proﬁle of phenethyl alcohol through a ﬁlm 8
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

2.5

 

 

[—0— Hum/day) I

Flux (glday) X E-2

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 56.Transmission proﬁle of benzyl acetate through a ﬁlm 8
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

77

 

  
 

 

 

 

 

 

3.5 i~

3..
'1‘
I" 2.5L
:4
5' 2(l
BI I-o—Fiux(glday)j
;; 1.51» g
.2
II. 14.

0.5

04; : ‘ ‘ + 1. : ‘ t . .

0 72 144 218 288 360 432 504 578 848 720

Run time (hours)

Figure 57.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #1 at 50°C and ﬂow rate of 20cclmin

 

 

L—o— Flux(glday)]

 

 

Flux (glday) X E-2 .

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 58.Transmlssion proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #1 at 50°C and ﬂow rate of 206cImin

78

 

,--.. --_. -. - ..
:O—Fluxmldayb

 

Flux (glday) X E—2

 

 

 

A; .L A

0 72 144 218 288 380 432 504 578 648 720
Run time (hours)

Figure 59.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #1 at 50°C and ﬂow rate of 206c/min

 

 

L—o— FquIo/dayll

 

Flux (glday) X E—2

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time ((hours)

Figure 60.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

79

_e
&

 

_A

N
A
'

d
L
v

9
cc

to— Flurry/<15”.

 

 

Flux (glday) X E-2
p o
# Ob

 

 

O ‘ . - * t A. 4. t -
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

, Figure 61 .Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

2.5

 

 

L—o— Flux(glday)ﬁI

 

Flux (glday) x 2.2

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 62.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #2 at 50°C and ﬂow rate of 20cclmin

80

 

 

,1 —o-:Fqu(g/day')j

 

Flux (glday) X E-2

 

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 63.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

 

 

 

 

 

 

 

 

1.4
‘2‘
III
at
‘3‘.
g [—0- Flux(glday) j
.5
IL

0 v t : : t ‘ : t 2 ¢

0 72.144 218 288 380 432 504 578 848 720
4, Run time (hours)

FigUre 64.Transmission proﬁle of phenethyl acohol through a ﬁlm C
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

8|

 

L;-°-"_"f_r_'9r_<g@a_vlj

Flux (glday) x E-2

 

 

 

0 L ¥ 4 g

0 72 144 218 288 360 432 504 578 648 720
Run time (hours)

Figure 65.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #3 at 50°C and ﬂow rate of 20cclmin

 

ﬁ—o—rﬁiﬁéﬁﬂ

 

Flux (glday) X E-2

 

 

 

O ‘ ‘ I i t - t : t .
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

ﬂ.

Figure 66.Transmission proﬁle of linalool through a ﬁlm C
from fragrance forrnuiation #4 at 50°C and ﬂow rate of 20cclmin

82

1.4

 

, [to-“511497980 5

 

Flux (glday) X E-2

 

 

 

0 f ‘4 ' r % 4 ‘4 *4 ‘f
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

 

Figure 67.Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #4 at 50°C and ﬂow rate of 200c/min

2.5

 

 

 

 

 

 

 

'2‘
III
at
3‘.
8
g L—o-Flux(glday)l
5
u.
0v A. : 4 4 t : r 4 4 .
0 72 144 218 288 360 432 504 576 648 720

Run time (hours)

Figure 68.Transmission proﬁle of benzyl acetate through a ﬁlm C
- from fragrance formulation #4 at 50°C and ﬂow rate of 20cclmin

83

 

TIME—7669)—

 

Flux (glday) X E-2

 

 

 

 

O ; t : 7 ‘ 4 ‘ v
0 72 144 216 288 360 432 504 576 648 720

Run time (hours)

Figure 69.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #5 at 50°C and flow rate of 20cclmin

 

 

1 -<>— Fqu(g/day)_f

 

Flux (glday) X E-2

l

 

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 70.Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #5 at 50°C and ﬂow rate of 2066/min

 

84

 

13.-0f. 'Lfluxeléarl'

Flux (glday) X E-2

 

 

 

0 .2 4 A ' : F : 4 4 .
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 71 .Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #5 at 50°C and ﬂow rate of 20cclmin

 

 

[-o—Fqum/dayﬂ

 

Flux (glday) X E-2
00

 

 

 

0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 72.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

85

 

0.4 ..

Flux (glday) X E-2 ‘

.°
N

 

A_ L J. A I

Run time (hours)

 

;. . _°_. _ 398919?!)

 

0 72 144 216 288 360 432 504 576 648 720

Figure 73.Transmission proﬁle of phenethyl alchol through a ﬁlm C
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

1.8

 

Flux (glday) X E-2

 

 

 

 

Run time (hours)

0 72 144 216 288 360 432 504 576 648 720

 

to- FquIg/d-yl I

Figure 74.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #6 at 50°C and ﬂow rate of 20cclmin

86

 

 

lL—o- Flux(glday)_j

 

Flux (glday) X E-2

 

 

 

O - * 4 * - s c t . .
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 75.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

1.2

 

Flux (glday) X E-2

l

 

 

 

 

0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

Figure 76.Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #7 at 50°C and ﬂow rate of 20cclmin

87

 

l_+__-ﬂe.<9199vil

Flux (glday) X E-2

 

 

 

0 : ‘ % 4 ' t ‘ : e 4.
0 72 144 218 288 380 432 504 578 848 720
Run time (hours)

 

Figure 77.Transmission proﬁle of benzyl aetate through a ﬁlm C
from fragrance formulation #7 at 50°C and ﬂow rate of 2006/min

 

 

l -o— Fqu(g/day)j

 

Flux (glday) x 2.2

 

 

 

O * : 4‘ *4 s 4 i 4 : .
0 72 144 216 288 360 432 504 578 648 720

 

Run time (hours)

Figure 78.Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

88

1.2

 

9
on

.0
O

 

r

:0— Fiuxlolday) .

 

Flux (glday) X E-2

 

 

 

 

0 72 144 218 288 360 432 504 578 648 720
Run time (hours)

Figure 79.Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #8 at 50°C and ﬂow rate of 20cclmin

 

 

[—0— Flux(glday) l

 

Flux (glday)X 2-2

 

 

 

O a. ‘4 r . - . - % : .
0 72 144 218 288 360 432 504 578 648 720
Run time (hours)

Figure 80.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #8 at 50°C and ﬂow rate of 206dmin

89

 

2.5 <

N

 

L‘°"'. -. . -I'E’SIJI‘EEYI

Flux (glday) X E-2

 

 

 

A. 4%

0 72 144 218 266 380 432 504 578' 848 720
Run time (hours)

0 v ‘ ’ + 1

Figure 81 .Transmission proﬁle of linalool through a ﬁlm C
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

 

 

Flux (glday) x 2.2

L—o— Flux(glday) j

 

 

 

O ; 2 ‘ 4 ‘ 4 4 : :
0 72 144 218 288 360 432 504 578 848 720
Run time (hours)

Figure 82.Transmission proﬁle of phenethyl alcohol through a ﬁlm C
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

90

1.8

 

L—o— FquE/d—EyT:

 

Flux (glday) X E-2

 

 

 

O f ‘4 ‘ - 4 4 t 4 .
0 72 144 218 288 380 432 504 576 848 720
Run time (hours)

Figure 83.Transmission proﬁle of benzyl acetate through a ﬁlm C
from fragrance formulation #9 at 50°C and ﬂow rate of 20cclmin

91

be expected to have high transmission rates through the polar ethylene-vinyl
acetate (EVA) ﬁlm structures.

in multi-component organic mixtures, like the fragrance fonnuiations, each
penetrant has the capacity of altering the transport properties of the co -
pentrants, which makes the mass transport process complicated. The inﬂuence
on the transport properties of one penetrant by another, as well as the constant
change in the driving force concentration and composition of organic mixtures
comprising the fragrance forrnuiations, are contributing factors to the complexity
of the mass transfer properties of the test systems studied.

A comparison of barrier characteristics of ﬁlms A, B, and C for the respective
probe compounds in the individual fragrance fon'nulations is presented
graphically in Figures 84-110 when ﬂux rate is plotted as a function of run time.
As the ﬁgures illustrate, the transmission rates for the respective probe
compounds, which exclude a-hexyl cinnamaldehyde, through ﬁlm A (vinyl
acetate content 6.5%) were signiﬁcantly lower than through ﬁlm B (vinyl acetate
content 9%) and ﬁlm C (vinyl acetate content 12%).

To further illustrate the barrier characteristics of the respective test ﬁlms to
the probe volatiles, the relative concentration of probe volatiles permeated
through selected fragrance formulation/polymer membrane systems as a
function of run time are presented graphically in Figures 111-113, respectively.
As demonstrated by both the transmission rate proﬁle curves (Figures 3-83) and

histograms presented in Figures 1‘11-113, the barrier properties vary signiﬁcantly 4

92

 

 

 

 

 

 

 

 

 

 

FIUXIQIday)-IIIIII A1 4 -— Fluxicldavléﬂim Bi? - 4 - fFIdMé/ﬁﬁ-ﬁléﬁﬁl
4
3.5 l» . ......
3
2.5I .'/‘~—-..“‘
E a. I ‘: \ \
3 2 ; I . \
e/ . . \h
g ' e . '~ ‘ \
u 1 5 1F °I e. . \
o" ‘ . ‘ ‘ \ \
‘ "I . . " . ‘7' - ‘
:1 . ‘ . . ‘ \
0 5 5" " - - . - x ‘
I 7......T~§“
0 A i : : 3 *ﬁ : ..... d
0 72 144 216 288 360 432 504 576 648 720
Run timeu‘om)

Figure 84. Comparsion of barrier charactieristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #1)

 

 

Flux(glday)—ﬁlm A - — - Flux(g/dey)-ﬁim e ------ Flux(gldey)-ﬁlrh?

 

1.4

1.2 1’ 4"

0.8‘I e ” ‘~~~/ ‘e \

Flux (glday)
2
/

0.8 3— - I ~ T .~.
0 . ‘ |\‘
0.4 » ' I

0.2 ‘I e,

 

 

 

0 72 144 218 288 380 432 504 576 848 720
Run time (hours)

Figure 85. Comparsion of barrier charactieristics of ﬁlm A. ﬁlm 8, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance forrnuiation #1)

93

 

 

 

 

 

f . _ .-- .-.-.. -__.__--._ ---._._. .
i Flux(glday)-ﬁlm A - - - Flux(glday)-ﬁlm e ------ Flux(glday)-ﬁirn 0‘]
2 . O
1.8 I’ 8. . . .
L61» :
1.4 i t. I § "‘ x \ “
A e I \‘
> 4.21 , ‘ \
a e I “. \
a 1 4° :’ .'.\\
z .1 ~. \\
2 0.8 1’ :I ‘ ‘\
u e, 7 I . \
0.8 1 - ‘ \
4., ~ . ' e \ ‘ s.
0.41-'I "-, ‘\
i \
0.2 .. . .‘ ~
0 - 4 t A 4 t ‘4 .‘r .....
432 504 578 648 720

 

 

0 72 144 218 288 360
Run time (hours)

Figure 86. Comparsion of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #1)

 

 

 

 

 

 

{—Fmg/daymm/I - - - Flux(glday)-ﬁim8 ------ Fqu(g/day)-mmcl
4
3.5
3 .' I- - - \
.‘I \
2.5 ., . \
r ‘ . \
E 2 0" ~ . “\s\
3 .” ‘~ \
5 0, e \ \
u 1 5 :I e. ‘ \
:I .‘ . . \ \ \
1 :I ‘ ‘ \ ~ ~
.‘I ‘ ‘\ \
0.5 1” . e . \
l ' ‘ ~ ~
0 A . L . . . '4' ----
218 266 360 432 504 578 848 720

Run time (hours)

Figure 87. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #2)

94

 

 

 

 

 

 

 

720

 

Flux(glday)—ﬁlmA — - - Fluxmldayyﬁlme ------ Fqu(g/day)—mmﬂ
1.4
1.2 o
. ‘K -----
1 . / \
. / \ , ___-
o. / \~‘~’.‘.’.l'--- \
E 08 » ,0 / \\
B .' / ' ' ° ‘ - ~\. .
* g 0.6 » ,' I \_‘_ ______
E ; I
L ' I . . ' -
0.4 ', / .
.‘l
0.2 ~-/
I
o : ' : i : : ; ;
o 72 144 216 288 360 432 504 576 648
Runtlms(hours)

Figure 88. Comparsion of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #2)

 

 

 

 

 

 

 

; Flux(glday)cﬁlmA - - — Flux(glday)oﬁlm8 ------ Hawk-Qinﬁﬂ
2.5
2 » .'
s. "’ ..“1- \
l ' ‘ ‘
.' I '. \
E1.5 4 : I s . ‘\‘\
3 " ‘~\
g :’ ‘~\.
c 1 :I ‘X
0" ‘\
g, ‘s\ \ \
o \
0.5 «- 9’ ‘ - a __ _
’3 . ‘ - . . . . \ \
o a ° ' 'c‘ """
o 72 144 216 288 360 432 504 576 648 720
Run time (hours)

Figure 89. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #2)

95

 

 

 

 

 

Flux(glday)-ﬁlmA — — - Flux(g/day)-ﬁlmB ------ Fqummm-m":07J
4.5
4 T ,.
3.5 J. E s
3 A
52.5 "' r.
E 2 -' ~
3 i.: -~~‘
u. ' \ .
1.5 4- ; x \ - . ,
1 : “-,~
U. ~.‘
0 5 w . N. \
288360432504576648720

 

 

O
i

72 144 216
Run tlms (hours)

0

Figure 90. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #3)

 

 

 

 

 

 

F'uxmmm _-.,- _tflEz‘ig’diﬂ-E'ME -- --:F.!ux<eié2:rr§'_m§
1.4 '
1.2 .. . : ----------- ~
1 r. / /\ \ " ' . . . “
s / \ ‘
o - _ __ / \ ‘I, a- " ‘ § ~
.' I ‘ “
E 0.8 . I . _ , .5 .\
3 ' \
v : I ‘\
g 0.5 1» . , ‘.\
IL :’ “\. .\
0.4 J 5’ ~ "
.‘I
."
0.2 L,’
288 360 432 504 575 648 720

Figure 91. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #3)

72 144

218

Run tlms (hours)

96

 

 

 

 

 

 

 

Flux(gldsy)-filmA - - - Flux(gldsy)-ﬁlmB ------ Fluxmldaymmc]
2.5
2 l
E 1.5 «»
3
.5 1 a. I ~ ~ ‘ \
II. I ‘ \
O \ Q
.0 ~ ~ 4 k
0.5 4» .' \ 5 \
.0 . ' \.‘ . .
0 1 ; r : : : t
144 216 288 360 432 504 576 648 720

O 72
Run tlms (hours)

Figure 92. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 3. and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #3)

 

 

 

 

 

 

 

Flux(gldsy)oﬁlmA - — - Flux(g/dsy)-ﬁlmB ------ Flux(gldsy)-ﬁlij
4
3.5 »
3 l '
- : /\ s .
. 2.5» : ,” \\‘.
a . ‘ .
a : I \ . s .
e 2 . \\
a .' ~ - _
E ‘.5 " ’ ‘ \
O ‘ \
.0 ‘ . . \ ‘
1 . ‘ ' - ‘~
0. ‘ . 0“ \ \ \
0.5 “O I . . ‘
.......... - g
0 * 4 f : v .
o 72 m 215 288 350 432 504 576 648 720
Run tlms (hours)

Figure 93. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8. and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #4)

97

Fluxg/day)-ﬁmA — JI-ﬁ‘u’xkgidayymnief ----- Flux(g/Eb})3ilth€!

 

 

 

Flux (glday)

 

648 720

 

432 504 576

288 360
Run tlms (hours)

 

 

72 144 218

Figure 94. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #4)

 

 

 

 

 

 

Flux(glday)-ﬁlmA — — - Flux(g/day)eﬁlm8 ------ Flux(glday)oﬁlmé:i
2
1.815
1.6 o // \~
1‘ // \
E 1.2 V I \' ‘.
3 1 r. :0. ~ ‘ .\.“\
g 0.8 ,' ‘ ‘ \ \ \
05 (. 3 "~.\.\\‘
0.4 .."-:“\\
0.2' T.‘.T‘~-
233 350 432 504 575 545 720

 

O

72 144 216
Run tlms (hours)

Figure 95. Comparsion of barrier characteristics of ﬁlm A. ﬁlm B, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #4)

98

 

Flux(glday).nin'i"4"-‘IIFIJiié/diy'ymme 4 - - - - 4‘Flux(giday)lnimc!

 

 

3.5

PM (sldavl

 

 

 

0 72 144 216 288 360 432 504 576 648 720
Run tlms (hours)

Figure 96. Comparsion of barrier characteristics of ﬁlm A, ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #5)

 

Fluxig/dmmm - - - Fuwiwmyrﬁjma ------ HQJGQF‘E

 

 

1.2

Flux (glday)

 

 

 

A A
T

o A A . .
21a 23a 360 432 504 575 648 720

0 72 144
Run tlms (hours)

Figure 97. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #5)

99

 

Flux(gldsy)-ﬁlmA — - — Flux(gldsy)-ﬁlm8 ------ Flux(gldsy)-ﬁlma]

g

 

 

PM! (9’61!)

 

 

 

0 72 144 216 288 360 432 504 576 648 720
Run tlms (hours)

Figure 98. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #5)

 

 

 

 

 

 

 

Flux(gldsy)-ﬁlmA — - - Flux(g/dsy)-ﬁlm8 ------ Fiuxgﬁﬂmﬁcj
4
\
35 J, I, \
\
3 L I \
I \
I .‘ . . \ \
A 2.5 “‘ I . \
~ \
5 I ~ \
3 2 I ~ . \
" \
g I . . .
I ‘. \
~ \
1 u I \\
I x
. \
0.5 + o
0 r ‘ V2 Y...°;’"“’:-7--
O 72 144 216 288 360 432 504 576 648 720
Run tlms (hours)

Figure 99. Comparsion of barrier characteristics of ﬁlm A. ﬁlm B, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #6)

lOO

 

Flux(g/dsy)-ﬁlmA — — — Flux(g/day)-ﬁlm8 ------ Hung/«37mg

 

I
l

 

 

 

 

 

o r A A be : ; .
0 . 72 144 216 288 380 432 504 576 648 720

Run tlms (hours)

Figure 100. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #6)

 

 

Flux(g/dsy)-ﬁlmA - - - Flux(gldsy)-ﬁlmi ------ mymm]

 

1.8 ‘L I \
1.6 tr I“ \
1.4 0

1.2 ”- I." “. \\
I; K \
g 1 9 ‘s‘ \

0.. "b I. ..g. ~~-\
.. I: ‘. \

0.5 . \

0.4 a ‘5.

0.2 >

 

 

0 72 144 216 288 380 432 504 576 648 720
Run tlms (hours)

Figure 101. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #6)

lOl

 

 

 

 

Flux(glday)-ﬁlmA - - - Flux(glday)-ﬁlm3 ------ FIUX(sldav)-ﬁlm€i

 

3.5

2.5 1)

Flux (WM)

1.5 - \

05> \~.;'._ I

 

 

 

0 - ‘ 5 ‘ t t - A ;
O 72 144 216 288 360 432 504 576 648 720
Run tlms (hours)

Figure 102. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #7)

 

qudwrnlm - — - Maid-Mme ------ Miami-am]

 

 

 

 

 

 

0 g - v . * t :
O 72 144 216 288 360 432 504 576 648 720
Run tlms (hours)

Figure 103. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #7)

 

 

 

 

T ammonium—J L: Fidiig/daymme ”5 éf-Tﬁiixiéldayﬁmhc '
2
K
1.8 1> I \
I"; \ \
1.6 4» ' x

Flux (elder)

 

9‘...
0.2» ~<; .....

 

‘

 

O - . . ‘T- "‘ “:--- «
0 72 144 216 288 360 432 504 576 648 720
Run time (hours)

Figure 104. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8. and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #7)

 

 

Humid-MM — - - Fluxmld-vl-MB ------ Mold-7W]

 

 

 

0 72 144 216 288 360 432 504 576 648 720
Run time (hours)

Figure 105. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #8)

l03

 

 

”unto/dawn!!!“ - -TFiu§(gl'J&iInirnBT--iFIdxﬁléJynnr—ia

 

 

 

 

 

1.4

Flux (glday)
.13 .o .-
O Q d N
I
I
r
l
\
I

.0
c

.0
N

 

 

 

0 Y -
0 72 144 216 288 380 432 504 576 648 720
Run time (hours)

Figure 106. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #8)

 

-— Woman-NM - - - Humid-Mme ------ summoning]

 

1.6
1.6 ~ I ‘

T
~
0

‘.“ e.\

1.2 .. I .‘ \

FM «I’M
/

0.6 4» \
0.6 {F ...... ~\

0.4 <

/

 

0.2 I» ‘ . ...... --

 

 

0 72 144 216 288 360 432 504 576 648 720
Run time (hours)

Figure 107. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #8)

 

 

 

 

 

F'UX(6/dav)-ﬁImA - — - Flux(gldsy)-ﬁlm8 ------ Fimmj

3.5
\
3 . \ \
\
t \

2.5 1r ‘. \ \

' \

\

N
/

PM (older)
I
/

 

 

 

1.5
\
1 ‘2
\\
0.5L ‘\
. ....... \__
0 2 . ""+°'ui
O 72 144 216 288 360 432 504 576 648 720
Runtlme(hours)

Figure 108. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
linalool vapor transmission proﬁle (fragrance formulation #9)

 

 

 

Fluxw/dlY—itﬁ'm - -_'_:_F'W(9’d'v)-”""3 """ ”ﬁlﬁtﬁmﬁ

 

 

 

 

 

 

 

0 72 144 216 288 360 432 504 576 648 720
Runtlme(hours)

Figure 109. Comparsion of barrier characteristics of ﬁlm A. ﬁlm 8. and ﬁlm C;
phenethyl alcohol vapor transmission proﬁle (fragrance formulation #9)

105

 

 

Flm(gldsy)-filmA — — — Flux(glday)-ﬁlm8 ------ Finis/dayi-ﬁlm

 

1.6 L I‘ ~ 2
1.6 «» , \

1-4 1’ \
1.2 ~ I \

Flux (glday)

0.3 .. I “, \
0.6 11»- . .0.
0.4 L

0.2 .. ' ‘

 

 

 

0 72 144 216 288 360 432 504 576 648 720
Run time (hours)

Figure 110. Comparsion of barrier characteristics of ﬁlm A, ﬁlm 8, and ﬁlm C;
benzyl acetate vapor transmission proﬁle (fragrance formulation #9)

106

rﬁlm A
Iﬁlm B
I ﬁlm C

Relative concentration (7.)
8

 

 

 

Time (hours)

Figure 111. Relative concentration of linalool permeated through ﬁlm A. ﬁlm 8,
and ﬁlm C permeated from fragrance formulation #2 at 50°C and
ﬂow rate of 20cclmin

sﬁlm C

=3

C

o

E

g ,__
g I ﬁlm A
3 I ﬁlm a
2

a

3

O

o:

 

 

 

72 216 360 504 648
Time (hours)

Figure 112. Relative concentration of phenethyl alcohol permeated through ﬁlm A,
ﬁlm B and ﬁlm C permeated from fragrance formulation #5 at 50°C and
ﬂow rate of 20cclmin

107

 

IﬁlmC

=3

1:

o

E

5 .____ ,_
o I ﬁlm A
c .
8 Iﬁlm B
2

=5

2

o

I!

 

 

 

72 216 360 ‘ 504 646
Time (hours)

Figure 113. Relative concentration of benzyl acetate permeated through ﬁlm A,
ﬁlm B and ﬁlm C permeated from fragrance formulation #8 at 50°C and
ﬂow rate of 20cclmin

l08

with time and membrane composition. This is further illustrated below where the
global loss and the percent loss of the individual probe volatiles are discussed.
The global loss through ﬁlm A, ﬁlm 8, and ﬁlm C were found to be approximately
45-50%. However, the relative rates of transmission of the respective probe
compounds through the test membranes varied as function of vinyl acetate
content of the EVA copolymers. It is assumed therefore, that the difference in
the relative transmission rates between each ﬁlm is due to the difference in
percent crystallinity of the ﬁlms. Polymer morphology refers to the physical state
by which amorphous and semi-crystalline regions coexist and relate to each
other and depends not only on its stereochemistry, but also on whether the
polymer has been oriented or not, and at which conditions of temperature, strain
rate, and cooling temperature the ﬁlm has been oriented, as well as the melt
cooling temperature.

Fundamental properties which are associated with polymer morphology
and will therefore inﬂuence the permeability and diffusivity characteristics of the
polymer include:
structural regularity or chain symmetry, which can readily lead to a three-
dimensional order of crystallinity. This is determined by the type of monomer(s)
and the conditions of the polymerization reaction.
chain alignment or orientation which allows laterally bonding groups to approach
' 'each other to the distance of the best interaction, enchanting the tendency to

form crystalline materials.

l09

Semicrystalline polymers consist of a microcrystalline phase dispersed in an
amorphous phase. The dispersed crystalline phase decreases the sorption of
penetrants, whenever the crystal conformations produce regions of higher
density than the amorphous polymer. A closer atomic packing tends to exclude
relatively large molecules such as organic perrneants. For this reason it is
generally accepted that gases and vapors are normally sorbed, and therefore
able to diffuse, only in the polymer’s rubbery or amorphous phase. The
dispersed microcrystals are impermeable to penetrant diffusion and create a
more tortuous path for the diffusing molecule. Additionally, the microcrystalline
phase also acts as a three dimensional crosslinking agent, increasing the non-
isotropism of the polymer. The combined decrease in sorption and diffusion
contributes then to a lower permeability.

According to the previous study by Matur(1993), ethylene vinyl acetate
copolymer(6.5% vinyl acetate) has a percent crystallinity of about 25.5, which is
considered highly amorphous.

The percent crystallinity was obtained by differential scanning calorimetry
analysis to give the heat of fusion (AHf) and substitution into Equation (23).

ActuaIHf (cal / g)
Theoretical 1 00% Hf (cal / g)

 

Percent crystallinity = x 100 (23)

The theoretical value of Hf was obtained from the literature. For
polyethylene(PE), the heat of diffusion value for the theoretical 100% crystalline
polymer was 68.4 cal/g (Troedel, 1984). For the respective vinyl
acetate/ethylene copolymers, it was assumed that the theoretical value for the

heat of fusion was equivalent to the PE value. The results of heat for fusion

110

deterrninations by differential scanning calorimetry (DSC), for the respective vinyl
acetate/ethylene copolymers, are presented in Appendix E. The percent
crystallinity of the test ﬁlms were 33.9% (65% vinyl acetate content), 31.3% (9%
vinyl acetate content) and 27.4% (12% vinyl acetate content) respectively.

The magnitude of the solubility for the penetrant in a polymer increases as
the molar volume of the condensed penetrant increases. The measure of
molecular size is the constant b of the Van der Waal’s equation of state, where b
is the effective volume of the molecules in one mole of gas. The molar volumes
of linalool, phenethyl alcohol, benzyl acetate and a-hexyl cinnamaldehyde are
177.3 cclmole, 119 cclmole, 144 cclmole, and 227 cclmole. Therefore, a—hexyl
cinnamaldehyde is expected to have the highest solubility in the polymer, . based
on concentration of the molar volume. However, the studied fragrance
formulations have low concentrations of a-hexyl cinnamaldehyde and
correspondingly low vapor pressure values, due to its high boiling point. Also,
there are other factors which can inﬂuence the mass transport properties of the
penetrants, like synergistic or antagonistic effects on permeability by co-
penetrants, temperature and penetrant-polymer interaction.

In general, the permeability increases with chemical similarities between the
components, for most penetrant-polymer systems. As the solubility parameters
of the penetrants and the polymer become closer, the solubility of the penetrant
in the polymer is expected to increase. The estimated solubility parameters of
linalool, phenethyl alcohol, benzyl. acetate and a-hexyl cinnamaldehyde are 5.2

(Cal/ems)”, 6.3 (Cai/cm’)”, 5.9 (Cal/cm3)"2, and 4.5 (Cal/cm3)"2 respectively.

Ill

Also, the solubility parameter of the ethylene/vinyl acetate copolymers is
estimated to be between 8.51 and 9.03 (Cal/cm3)1'2_ Therefore, it is expected
that phenethyl alcohol and benzyl acetate would have a higher solubility in the
ethylene/vinyl acetate (EVA) copolymers than linalool and a-hexyl
cinnamaldehyde. However, it was found that linalool and benzyl acetate had
higher ﬂux values than phenethyl alcohol and a-hexyl cinnamaldehyde through
the EVA copolymers. This is due to the fact that permeability through a polymer
membrane is affected not only by solubility but also by diffusivity and vapor
pressure of the penetrant.

Furthermore, plasticization of the polymer by the'sorbed penetrant can result in
changes the polymer structure because of swelling and distortion of amorphous-
region incurred during sorption(Rogers, 1969). In this regard, sorption of the
penetrant vapors may disrupt the initial local conformation of crystalline and
amorphous regions, so that the effective density and local molecular
conformation vary in a nonlinear fashion both with time, and as a function of
distance in the sample (Rogers, 1964).

The concentration of organic penetrants is also important in
understanding the permeability of organic vapor/barrier membrane combinations.
The free volume theory can be used to explain the concentration and
temperature dependency of the diffusion coefﬁcient, characteristic of organic
vapors in amorphous polymer above their glass transition temperature (Tg)
(Meares, 1958, and Fujita et al., 1960). According to the free volume theory, for

polymer/penetrant system the mobility of both the polymer chain segments and

112

diffusant molecules is primarily determined by the free volume of the system.
Therefore, the concentration dependency of the diffusion coefﬁcients for
polymer/organic vapor systems can be attributed to the extreme sensitivity of the
mobility of diffusant molecules and polymer chain segments to a slight change in
the average free volume in the system. Also, the free volume theory can be
applied to the idea of competition for sorption sites between components of a
mixture. In a multi-component organic mixtures like the fragrance formulations
studied, each organic component would compete for active centers within the
polymer bulk phase. The sorption of one component may reduce the

’ permeability of a second component by effectively reducing the microvoid
content and diffusion pathway through the polymer. Factors such as the number
of components competing to occupy the available active sites, the change in the
driving force concentration, the concentration and temperature dependency of
the mass transport process, and the physicochemical characteristics of the
components involved in the mass transport process all contributes to the

complexity of the transport properties of the fragrance volatiles in the system.

|13

STATISTICAL ANALYSIS

The results of Simple Factorial and One-way ANOVA for each dependent
(four probe compounds) are presented in Appendix D.
As indicated in Appendix D, the main effect of the three variables (ﬁlm, solvent,
thickening agent) is presented as a value of signiﬁcance level. The signiﬁcance
level is the basis for deciding whether or not to reject the null hypothesis. If the
. observed signiﬁcance level is less than 0.05 or 0.01, the null hypothesis is
rejected, which means that the variable has a signiﬁcant effect. For each probe
compound, the results of the analysis suggest that it is the ﬁlm group that has
the most signiﬁcant effect on the permeability of the fragrance delivery system, .
when compared to both the solvent group and thickening agent group, due to the
less than 0.05 signiﬁcance level, obtained for these groups. After deciding that
the ﬁlm group had a signiﬁcant effect rather than solvent (lsopar) and thickening
agent (Cabosil) on the permeability of the fragrance delivery system, a One-way
ANOVA procedure (regression) was applied to determine the barrier properties
of each ﬁlm for the probe compounds.
Figures 118-120 presents graphically the relationship between the median slope
values(AFlux/At) obtained from the transmission proﬁle plots of linalool, ‘
phenethyl alcohol and benzyl acetate for the respective fragrance formulation as
'a function of vinyl acetate content of three EVA ﬁlms evaluated. As shown, the
change in rate with time (AFqu/At) for the respective probe volatiles increases

linearly with an increase in vinyl acetate content.

SUMMARY AND CONCLUSIONS

The effect of membrane composition and fragrance formulation
composition on the permeation of selected fragrance volatiles through an
ethylene vinyl acetate(EVA) copolymer membrane based fragrance delivery
system was studied by an isostatic method. (The permeation rates of selected
fragrance volatiles present in the fragrance formulations, to include: linalool,
phenethyl alcohol, benzyl acetate and a-hexyl cinnamaldehyde, were determined
as a function of time at 50°C and a constant air ﬂow rate of 20cclmin, over a four
week period.

Permeability studies were carried out at 50°C at constant carrier gas flow rate of.
20cclmin to insure that the mass transport process is diffusion controlled. A
three level, three variable statistical design experiment was carried out to
evaluate the three variables(vinyl acetate content in the EVA copolymer,
thickening agent content and dispersing solvent content of the fragrance
formulations) and their effect on the permeability of fragrance probe volatiles
through the fragrance delivery system membrane. A total of nine different
fragrance formulations and three EVA membranes were evaluated in the
experimental design.

The transmission rates of all probe volatiles through the three test polymer
structures were found to be dependent on the partial pressure of the respective
fragrance volatiles, which acts as the driving force for the permeation of probe

compounds from the fragrance formulations. The ﬁnite concentration of the

114

115

fragrance volatiles, the constant change in the driving force concentration and
composition explain the transmission proﬁle curves obtained. From the
transmission proﬁle data, linalool showed the highest transmission rate when
compared to phenethyl alcohol, benzyl acetate, and a-hexyl cinnamaldehyde .
Linalool is present in the highest concentration in the fragrance formulation and
has the highest vapor pressure value, which explains the observed higher
transmission rate of linalool. Also, a-hexyl cinnamaldehyde was not detected in
the permeated vapor stream, which can be explained by its low concentration in
the fragrance formulation and high boiling point(i.e. low vapor pressure).

The global or total loss of volatiles from the fragrance formulations
following termination of the permeability studies was between 45-50% for the
three test membrane structures. Linalool, benzyl acetate and phenethyl alcohol
showed losses greater than 85%, while a—hexyl cinnamaldehyde showed a
percent loss of approximately 50% for the three test ﬁlms. Statistical analysis
showed that the vinyl acetate content of the test membrane was a signiﬁcant
variable effecting the permeation rates of fragrance volatiles through the
fragrance delivery system. Film Methylene vinyl acetate content 6.5%) was
found to have signiﬁcantly lower transmission rates for the respective probe
compounds when compared to Film B(vinyl acetate content 9%) and Film C(vinyl
acetate content 12%).

In terms of practical importance, from the study of the permeation of the
constituents of multi-component organic fragrance formulations through ,

polymeric barrier membranes, a relative comparison of barrier properties of

ll6

polymeric packaging materials to organic penetrants of varying molecular
structure can be made. Furthermore, as a results of this study, a better
understanding can be achieved with respect to the effect of the chemical nature
of the fragrance delivery system membrane and fragrance formulation on
fragrance volatiles permeability. This knowledge can then be applied to optimize

the design of a plug-in type air freshener system to provide the required end-use

life.

FUTURE RESEARCH

Numerous, future studies could be conducted which could lead to an
increased understanding of the mass transport properties of multi-component,
organic vapor mixtures. Studies of the relationship between membrane structure
and barrier properties will be important in the development and/or selection of
polymeric materials for speciﬁc solutions and transport applications. In the
fragrance delivery system studied, there was a constant change in the partial
pressure gradient or the driving force and ﬁlm structure as a function of time.
Detailed studies on the effect of changes in the vinyl acetate composition of the
test ﬁlms may be necessary to gain a better understanding of, and make relative
comparisons between, polymeric packaging materials of varying molecular

structure used as barriers to organic penetrants.

in

APPENDICES

Appendix A

Gas Chromatograph Calibration Procedure

Equipment:

10 ml volumetric ﬂasks with stoppers (20)

100 ml volumetric ﬂasks with stoppers (4)

10 pl liquid sampling syringes

10 ml pipettes with automated pipette ﬁxtures
Materials

Linalool

Phenethyl alcohol

Benzyl acetate

Alpha Hexyl Cinnamaldehyde

Methanol

Concentrations of 1,4,10,20,50, and 100 PPM (vlv) of probe

compounds in methanol were used to create the calibration curves.

Procedure

In all cases, a standard curve of area response vs. Quantity
injected was constructed form standard solutions of known concentration. The
solutions were prepared by dissolution of known quantities of probe compounds

in methanol. The following procedure was followed:

118

119

1. The volumetric ﬂasks, pipettes and syringes were baked in an oven at
135°C for 12 hours prior to used to remove any residual solvent or perrneant and
cooled to room temperature.
2. The purity of the solvent is evaluated by using the gas chromatograph to
ensure that there are no interfering peaks at the retention times of the probe
compounds.
3. The following dilution scheme is adopted for preparing the standard
solutions:

a. The 100 ml volumetric ﬂask is partially ﬁlled with methanol.

b. 10 pl of the probe compound is added.

c. Stoppered and slightly swirled to mix.

d. The ﬂask is ﬁlled to volumetric line with solvent.

e. The. contents of the ﬂask are mixed.

This provides the 100 PPM stock solution. From this solution, the other

concentrations are obtained. For example:

(a). A 10 ml volumetric ﬂask is partially ﬁlled with solvent using a pipette.

(b). The stock solutions swirled to ensure proper mixing.

(c). 1 ml of the stock solution is added to the 10 ml volumetric ﬂask and
ﬁlled to volumetric line with solvent.

(d). The contents of the ﬂask are mixed.

This provides 10 PPM concentration. The other concentrations are

obtained similarly.

120

4. The GC conditions, as indicated in the Material and. Methods section were
used.

5. 1 pl of samples were injected directly into the gas chromatography and
the area response recorded.

The analyses were done in duplicate and average area response recorded.

6. From he density values of the respective probe compounds, the quantity
injected was determined.

V/v X volume injected X p = mass injected

7. The average of replicate analyses was taken and the area response is
plotted vs.‘The quantity (9) injected for each samples for the respective
compounds. The values obtained, and the calibration factor are tabulated. The

reciprocal of the slope of the line gives the calibration factor.

Table 11. CALIBRATION DATA FOR LINALOOL

(Retention Time = 10.64 min.)

 

 

 

 

 

 

 

Quantity x 10'9 Area Response Calibration factor (g/AU)
0.87 6931
3.48 15361
8.7 46915 2.2027 x 10'”
17.4 78084
43.5 200412

 

 

 

Table 12. CALIBRATION DATA FOR PHENETHYL ALCOHOL

(Retention Time = 11.03 min.)

 

 

 

 

 

 

 

Quantity x 10% Area Response Calibration factor (gIAU)
1.023 8890
4.092 19960
10.23 56810 2.0241 x 10‘13
20.46 105564
51.15 255381

 

 

 

 

 

122

Table 13. CALIBRATION DATA FOR BENZY L ACETATE

(Retention Time = 12.78 min.)

 

 

 

 

 

 

 

Quantity x 10'9 Area Response Calibration factor (glAU)
1.04 . 2619
4.16 12597
10.4 33336 3.1514 x 10“:
20.8 77547
52.0 163454

 

 

 

Table 14. CALIBRATION DATA FOR a-HEXYL CINNAMALDEHYDE

(Retention time = 31.53 min.)

 

 

 

 

 

 

 

Quantity x 10r Area Response Calibration factor (glAU)
0.95 3480
3.86 9335
9.5 28596 2.9644 x 10'13
19 58913
47.5 158656

 

 

 

 

 

A.U'E+2

A.U‘E+2

2500

25001

 

 

y = 45.398x + 23.965
R’ = 0.9962

 

 

5 10 15 20 25 30 35 40
quantity '5! (g)

Figure 114. Calibration curve for linalool

 

 

 

y = 49.4041: + 34.031
12’ = 0.9994

 

1o 20 30 4o 50
90mm! ‘5-9 (9)

Figure 115. Calibration curve for phenethyl alcohol

 

 

A.U‘E+2

A.U"E+2

124

 

  
 

1600
1600 1

y . 31.731x 4 18.111
“00 ‘ R’ . 0.993

 

1200
1000
800 1

400
200

 

 

 

0 10 20 30 40 50 80
quantltv ‘E-9 (9)

Figure 116. Calibration curve for benzyl acetate

 

1400 j
y . 33.733x - 27.24
12°° j R2 . 0.9969

 

 

 

o - 2 - - -
0 10 20 30 4O 50
qusntlty 'E-O (9)

Figure 117. Calibration curve for alpha-hexyl cinnamaldehyde

Appendix B
Vapor pressure and vapor activity

One ml of Linalool, Phenethyl alcohol, Benzyl acetate, Alpha hexyl
cinnamldehyde, and the fragrance formulations 1-9 were added to 25 ml septa
seal vials. The vials were sealed with Teﬂon coated silicone septa and
aluminum crimp cap. They were then allowed to equilibrate at 50°C. 200 pl of
the headspace of these samples was taken and injected directly into the gas
Chromatograph for quantiﬁcation after an equilibration period of 5 days. Five
repetitions of each vial were done, making sure to allow equilibrium at
temperature before the next injection. For fragrance formulations , 50 pl of the
head space was used for analysis.

The average area response is converted to concentration by the following

equaﬁon:

area response X calibration factor X (Vin—j) = conc.

The saturation vapor concentration was then converted to its corresponding
saturation vapor pressure using the ideal gas law: PV = nRT
The saturation vapor pressure values for the respective probe compounds are in

table and the plots of temperature vs. Vapor pressure are shown in Figure

respectively.

125

126

Vapor activity of the probe compound in the fragrance formulation was
calculated by dividing the vapor pressure of the probe compound in the
fragrance formulation at a temperature by saturation vapor pressure of the pure
compound.

a=PlPo

|27

APPENDIX C

DATA ON THE TRANSMISSION RATES OF THE PROBE VOLATILES FROM

FRAGRANCE FORMULATION 1 - 9 THROUGH FILM A, FILM B, AND FILM C

AT 50°C

. Table 15. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 1 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 1 .4550 0.4993 0.9373 0
144 1.2504 0.3773 0.8533 0
216 1.2073 0.4211 0.7935 0
288 1 .2403 0.6067 0.7653 0
360 0.6402 0.3653 0.3901 0
432 0.5579 0.4785 0.3142 0
504 0.5449 0.5549 0.2332 0
576 0.5487 0.5572 0.1934 0

. 648 0.3659 0.5034 0.1532 0
720 0.2986 0.3850 0.1036 0

 

 

[28

Table 16. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 2 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

Hours

 

 

 

 

 

 

 

 

 

 

 

Linalool Phenethyl Benzyl acetate a-Hexyl
. alcohol cinnamaldehyde
72 1.2564 0.3804 0.9163 0
144 1 .6704 0.5898 0.9798 0
216 1.2996 0.6009 0.7658 0
288 1.0518 0.6828 0.6438 0
360 0.7265 0.6307 0.4543 0
432 0.6008 0.7933 0.4041 0
504 0.3486 0.5973 0.2269 0
576 0.1848 0.3812 0.1131 0
648 0.2038 0.4612 0.1135 0
720 0.2213 0.5292 0.1059 0

 

 

 

 

 

 

[29

Table 17. Flux (g/day) X E-2 as a function of run time for probe compounds from

fragrance formulation 3 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a—Hexyl
alcohol cinnamaldehyde

72 2.2964 0.5356 0.2912 0
144 1.7353 0.4829 0.9468 0
216 1.6111 0.6201 0.8034 0
288 1.1386 0.4614 0.5441 0
360 0.8391 0.4486 0.3828 0
432 0.4358 0.4146 0.1885 0
504 0.5268 0.5929 0.1955 0
576 0.2359 0.4754 0.08944 0
648 0.1864 0.4801 0.0537 0
720 0.0562 0.2274 0.0335 0

 

 

 

 

 

 

Table 18. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 4 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 2.3297 0.8529 1.1849 0
144 1.3024 0.3987 0.6380 0
216 1.2253 0.5142 0.6081 0
288 0.9181 0.4796 0.4247 0
360 0.7345 0.4966 0.3233 0
432 0.5347 0.5111 0.2284 0
504 0.2822 0.5145 0.1395 0
576 0.5699 0.7243 0.1906 0
648 0.5111 0.8250 0.1524 0
720 0.0651 0.2392 0.0372 0

 

 

 

 

 

 

131

Table 19. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 5 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
BIOONOI cinnamaldehyde
72 2.3377 0.8163 1.1531 0
144 1.7458 0.7375 0.9511 0
216 1.2686 0.5291 0.6875 0
288 1.1918 0.5774 0.5938 0
360 0.8308 0.5090 0.4032 0
432 0.5217 0.4472 0.2393 0
504 0.7295 0.7644 0.2906 0
576 0.6950 0.5281 0.2462 0
648 0.2763 0.5873 0.1034 0
720 0.2240 0.5661 0.0659 0

 

 

 

 

 

 

Table 20. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 6 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 2.6060 0.9730 1 .3097 0
144 1.7956 0.6024 0.9064 0
216 1.4344 0.6359 0.7525 0
288 1 .1552 0.4904 0.5539 0
360 0.9429 0.4493 0.4176 0
432 0.6966 0.5345 0.3148 0
504 0.5233 0.5417 0.2307 0
576 0.4181 0.5604 0.1597 0
648 0.2187 0.5588 0.1196 0
720 0.1 137 0.4976 0.0766 0

 

 

 

 

 

 

I33

Table 21. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 7 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 2.9323 0.9930 1.6167 0
144 2.3981 0.9398 1 .3992 0
216 1.9881 0.8268 1.1936 0
288 1.4881 0.6968 0.8144 0
360 1.3092 0.7513 0.6817 0
432 0.8151 0.6998 0.3851 0
504 0.7998 0.9198 0.3522 0
576 0.5714 0.8702 0.2392 0
648 0.3430 0.5225 0.1429 0
720 0.2078 0.5042 0.0886 0

 

 

 

 

 

 

l34

Table 22. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 8 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.069 1 .2482 1 .5387 0
144 2.3270 1 .0699 1 .2322 0
216 1.8286 1.8683 1.0008 0
288 1.7848 0.9159 0.9211 0
360 1.2912 0.8862 0.6147 0
432 0.8169 0.6811 0.3968 0
504 0.6394 0.6603 0.2731 0
576 0.4439 0.6953 0.1869 0
648 0.2513 0.6267 0.0919 0
720 0.1415 0.5162 0.0432 0

 

 

 

 

 

 

135

Table 23. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 9 through ﬁlm A at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
3'0000' cinnamaldehyde

72 3.2692 1 .2059 1 .6046 0
144 2.4098 0.9689 1.3975 0
216 1.9533 0.7621 1.0846 0
288 2.0223 0.9766 1 .0366 0
360 1 .4650 0.8261 0.7072 0
432 1 .0987 0.7581 0.5380 0
504 * 0.8442 0.7935 0.4072 0
576 0.4620 0.7117 0.2176 0
648 0.3058 0.7380 0.1289 0
720 0.1975 0.6107 0.0688 0

 

 

 

 

 

 

I36

Table 24. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 1 through ﬁlm B at a cell ﬂow rate of 20 cclmin at 50°C

 

Linalool

 

 

 

 

 

 

 

 

 

 

 

Hours Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 2.6188 0.7561 1.4484 0
144 2.5145 0.8372 1.3945 0
216 2.3177 0.8010 1.2295 0
288 1.8158 0.7620 0.9553 0
360 1.6620 0.9812 0.8214 0
432 1.0640 0.9843 0.5310 0
504 0.8572 1 .1 109 0.4289 0
576 0.4381 0.6576 0.2359 0
648 0.3140 0.6027 0.1733 0
720 0.1 157 0.4589 0.0811 0

 

 

 

 

 

 

l37

Table 25. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 2 through ﬁlm B at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
3'0000' cinnamaldehyde
72 2.9649 0.8004 1 .7593 0
'144 2.9274 1.0962 I 1.7904 0
216 2.1213 0.9020 1.2657 0
288 1 .5099 0.8508 0.7648 0
360 1.2393 0.9127 0.6062 0
432 ' 0.9713 0.9194 0.4706 0
504 0.7945 0.9297 0.4051 . 0
576 0.3390 0.5661 0.1639 0
648 0.2118 0.5798 0.1049 0
720 0.1697 0.5720 0.0939 0

 

 

 

 

 

 

138

Table 26. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 3 through ﬁlm 8 at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 2.1230 0.8759 1.1671 0
144 1 .9884 0.8938 1 .0776 0
216 1 .8298 1 .0655 0.9673 0
288 1 .2073 0.8723 0.7236 0
360 1 .2430 0.9199 0.6574 0
432 0.7901 0.8685 0.4246 0
504 0.3713 0.7848 0.1923 0
576 0.2744 0.5637 0.1400 0
648 0.1397 0.4565 0.0761 0
720 0.0827 0.4352 0.0514 0

 

 

 

 

 

 

l39

Table 27. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 4 through ﬁlm 8 at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 2.4922 0.9881 1 .2603 0
144 2.7803 0.9810 1.6924 0
216 2.0444 0.9701 1.0791 0
288 1.6547 0.8263 0.9694 0
360 1.5470 1.1065 0.7520 0
432 1 1.1257 0.9802 0.5434 0
504 0.8642 0.8042 0.4501 0
576 0.6176 0.7474 0.3106 0
648 0.4315 0.7189 0.2182 0
720 0.3013 0.7828 0.1599 0

 

 

 

 

 

 

I40

Table 28. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 5 through ﬁlm 8 at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 2. 5826 0.7804 1 .5957 0
144 2.2964 0.9879 1.2642 0
216 2.1542 0.8983 1.2768 0
288 1 .4258 0.8479 0.7326 0
360 1 .5624 1 .0702 0.8234 0
432 1 .0466 0.8343 0.5598 0
504 0.5618 0.8119 0.3075 0
576 0.4332 0.7609 0.2074 0
648 0.3011 0.6952 0.1337 0
720 0.1532 0.6128 0.0771 0

 

 

 

 

 

 

l4]

Table 29. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 6 through ﬁlm B at a cell flow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 3.6820 1.2169 1.9547 0
144 2.7266 1.0068 1.7162 0
216 2.2795 0.9546 1.2687 0
288 1.5436 0.8284 0.8286 0
360 1 .4305 1 .0670 0.7853 0
432 0.9042 0.8568 0.4807 0
504 0.5217 0.7776 0.2628 0
576 0.3597 0.6787 0.1828 0
648 0.1444 0.5624 0.0799 0
720 0.0938 0.5812 0.0491 0

 

 

 

 

 

 

I42

Table 30. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 7 through ﬁlm 8 at a cell flow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.2675 1 .1575 1.8862 0
144 2.7973 1.0763 1.6083 0
216 2.0816 1.1275 1.1756 0
288 1.4301 0.9231 0.7942 0
360 0.9947 1 .0284 0.4775 0
432 0.4679 0.7543 0.2389 0
504 0.3161 0.6948 0.1520 0
576 0.5612 0.6488 0.0699 0
648 0.1189 0.6109 0.0574 0
720 0.0643 0.5376 0.0362 0

 

 

 

 

 

 

 

143

Table 31. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 8 through ﬁlm 8 at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.5354 1 .2401 1 .7699 0
144 1.7325 1.0302 1 .4669 0
216 1.9545 0.8257 1.1456 0
288 1 .8645 0.9807 1 .0707 0
360 1.2412 0.8549 0.6645 0
432 1.1164 0.9716 0.5981 0
504 0.5987 0.7965 0.3170 0
576 0.3446 0.6654 0.1934 0
648 0.3194 0.7210 0.1554 0
720 0.1934 0.6352 0.0963 0

 

 

 

 

 

 

144

Table 32. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 9 through ﬁlm 3 at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.2999 1.1334 1.8565 0
144 2.8553 0.9741 1.7866 0
216 2.3657 1.0362 1.3604 0
288 1.8124 0.9697 0.9719 0
360 1 .4690 0.9640 0.8058 0
432 1 .0203 0.8967 0.4967 0
504 0.7841 0.9239 0.3927 0
576 0.5753 0.8582 0.2799 0
648 0.2321 0.6436 0.1220 0
720 0.1588 0.6860 0.0753 0

 

 

 

 

 

 

 

I45

Table 33. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 1 through ﬁlm C at a cell flow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.5185 1.0536 1.9594 0
144 3.3461 1.2100 1.8157 0
216 2.0232 0.8318 1.1202 0
288 1.5165 0.8353 0.8145 0
360 1.1638 0.9701 0.6132 0
432 0.8300 0.9191 0.4207 0
504 0.4582 0.7608 0.2639 0
576 0.2119 0.5215 0.1278 0
648 0.1317 0.5828 0.0799 0
720 0.0596 0.4124 0.0382 0

 

 

 

 

 

 

I46

Table 34. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 2 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
3'0000' cinnamaldehyde
72 3.6904 1 .2454 2.2206 0
144 2.5171 1.1017 1.5864 0
216 2.0142 1.0521 1.2102 0
288 1 .2623 0.9264 0.6647 0
360 0.8720 0.8781 0.4612 0
432 0.5071 0.7297 0.2791 0
504 0.3183 0.7232 0.1696 0
576 0.1649 0.6420 0.1044 0
648 0.0850 0.4526 0.0660 0 .
720 0.0410 0.3819 0.0283 0

 

 

 

 

 

 

 

I47

Table 35. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 3 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 4.0343 1 .2336 2.4080 0
144 3.3757 1.2162 2.0313 0
216 2.4026 1.1867 1.3710 0
288 1.6284 0.9958 0.8750 0
360 1 .3392 1 .0750 0.6859 0
432 0.6921 0.7668 0.3794 0
504 0.4899 0.7899 0.2608 0
576 0.1976 0.5119 0.1255 0
648 0.1120 0.4647 0.0726 0
720 0.0631 0.4323 0.0440 0

 

 

 

 

 

 

I48

Table 36. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 4 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde
72 3.7183 1.1415 1.9071 0
144 3.1424 1.0688 1.7064 0
216 2.4074 0.9669 1.2559 0
288 1.8283 1.0379 0.9506 0
. 360 1.2352 0.8202 0.6232 0
432 0.9304 0.9495 0.4570 0
504 0.4782 0.6941 0.2687 0
576 0.2583 0.6527 0.1587 0
648 0.1757 0.5643 0.1026 0
720 0.0799 0.5265 0.0485 0

 

 

I49

Table 37. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 5 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.2000 0.9572 1 .6889 0
144 2.3113 0.8499 1.2986 0
216 2.0746 0.9010 1.0394 0
288 1 .6570 0.8593 0.8435 0
360 0.7807 0.621 1 0.4077 0
432 0.6507 0.6927 0.3178 0
504 0.2658 0.5222 0.1520 0
576 0.1634 0.4956 0.0879 0
648 0.0882 0.4115 0.0474 0
720 0.0445 0.3080 0.0293 0

 

 

 

 

 

 

I50

Table 38. Flux (glday) X E—2 as a function of run time for probe compounds from

fragrance formulation 6 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
8'0000' cinnamaldehyde

72 2.7368 0.9971 1.5543 0
144 2.2818 0.9531 1.2966 0
216 1.7137 0.8681 0.9108 0
288 1.4347 1 .0034 0.6903 0
360 0.7017 0.7919 0.3414 0
432 0.2820 0.5591 0.1569 0
504 0.1838 0.6236 0.0979 0
576 0.0672 0.4616 0.0418 0
648 0.0406 0.3768 0.0217 0
720 0.0137 0.2624 0 0

 

 

 

 

 

 

151

Table 39. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 7 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 3.3643 1 .0748 1.7388 0
144 2.3514 0.8499 1.3146 0
216 1.9420 0.8033 1.0031 0
288 1 .5437 0.8463 0.7593 0
360 1.0653 0.8446 0.5184 0
432 0.6210 0.6641 0.3051 0
504 0.3670 0.6815 0.1963 0
576 0.2338 0.6914 0.1199 0
648 0.1065 0.4834 0.0597 0
720 0.0741 0.4244 0.0368 0

 

 

 

 

 

 

I“

«.4-

Table 40. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 8 through ﬁlm C at a cell flow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
alcohol cinnamaldehyde

72 2.9128 0.9446 1.4785 0
144 2.5386 0.8723 1 .3599 0
216 1.9743 0.8017 0.9586 0
288 1.2417 0.6314 0.6107 0
360 1.1273 0.8151 0.5406 0
432 0.7540 0.8133 0.3679 0
504 0.4442 0.6777 0.2103 0
576 0.2842 0.7276 0.1310 0
648 0.1358 0.5973 0.0708 0
720 0.0845 0.3712 0.0372 0

 

 

153

Table 41. Flux (glday) X E-2 as a function of run time for probe compounds from

fragrance formulation 9 through ﬁlm C at a cell ﬂow rate of 20 cclmin at 50°C

 

 

 

 

 

 

 

 

 

 

 

 

Hours Linalool Phenethyl Benzyl acetate a-Hexyl
811(3000I cinnamaldehyde
72 .3-0701 1.2779 1.6235 0
144 1.8263 0.7999 1.0848 0 .
216 1.3138 0.6097 0.7478 0
288 1 .0272 0.6493 0.5842 0
360 0.7873 0.6444 0.4341 0
432 0.6031 0.6865 0.3313 0
504 0.3046 0.5471 0.1821 0
576 0.1460 0.3866 0.1016 0
648 0.0736 0.3663 0.0510 0
720 0.0439 0.2992 0.0297 0

 

 

 

 

 

 

APPENDIX D.

STATISTICAL ANALYSIS

154

155

Table 42. Slope of transmission proﬁle curve

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Variable No Linalool Phenethyl Alcohol Benzyl Acetate
1 -0. 1337 0.003 -0.1035
2 -0.166 00046 01086
3 -0.2431 —0.01 91 -0. 1356
4 -0.1897 -0.0083 -0.1016
5 -0.2053 -0.017 -0.1511
6 02466 -0.0286 -0.1251
7 02942 -0.0393 -0.1758
8 -0.3143 -0.0699 —0.1677
9 03256 -0.0475 -0.1763

10 —0.3077 -0.0241 -0.1678
11 0.3363 0.0431 0.2031
12 02548 00597 01395
13 -0.2793 -0.0302 -0.1566
14 02865 00278 —0.1725
15 03862 00641 -0.2184
16 03579 00739 02133
17 03578 00536 01899
18 03583 00451 -0.2129
19 -0.4012 -0.0726 -0.2197
20 -0.3777 -0.0917 -0.2277
21 04465 -0.1016 -0.2628
22 -0.4158 -0.0699 -0.2161
23 03504 -0.072 01856
24 03188 00852 -0.1771
25 03506 0.0585 -0.1844
26 03242 00444 -0. 1667

-0.2891 -0.0801 0.1578

27

 

 

 

 

 

Table 43. RESULTS OF ANALYSIS OF VARIANCE

_l

 

 

 

 

       

 

 

 

 

 

 

 

Linalool Phenethyl alcohol Benzyl acetate

Main Effects .007 .001 .014

Film Group .001 .000 .002

Solvent Group .687 .067 .787

Thickening Agent Group .246 .176 .332

-l I“I“
Film And Solvent Group .425 .7334 .891
Film And Thickening Agent .029 .018 .025
Group I

Solvent And Thickening .868 .4336 .814

Agent Group

 

 

 

 

 

 

157

 

 

 

 

 

e 17 0 9 | 10 ' 1'1 12

Film (vinyl acetate content)
Figure 118. Comparsion of barrier characteristice of ﬁlm content
(linalool)

13

[58

 

-.101 o

-.12

 

 

 

s 7 6 9 1'0 1'1 12
Film (vlnyf acetate content)
Figure 119. Comparsion of barrier characteristics of ﬁlm content
(phenethyl alcohol)

 

13

159

 

0.0

 

 

 

 

s 7 9 9 . 10 1'1 1'2

Fllrn(vlnyl acetate content)
Figure 120. Comparsion of barrier characteristics of ﬁlm content
(benzyl acetate)

13

 

APPENDIX E

Melt proﬁle of ﬁlm samples
The melt proﬁle of ﬁlm samples ﬁlm A(6.5% vinyl acetate content), ﬁlm B(9%
vinyl acetate content) and ﬁlm C(12% vinyl acetate content) were determined by
Differential Scanning Calorimetry (DSC) analysis. Analysis was carried out on a
Dupon 9900 computer/thermal analyzer. The melt proﬁle of the ﬁlms are shown

in Figures , and the melt temperatures of the ﬁlms are summarized below:

Film sample Heat of Melt Percent
fusion(J/g) temperature(°C) crystallinity
Film A 97.17 102.35 33.93
Film 8 89.54 102.98 331.27
Film C . 78.48 94.47 27.39

I60

161

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162

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“Illllllllllllllllllllllll