STUDIES ON BARRIER PROPERTIES OF FILMS OF LDPE/PVA BLENDS FOR FOOD PACKAGING APPLICATION

Presented by :- RAJENDRA KUMAR Under the supervision of Prof. S.N.Maiti Centre for Polymer Science and Engineering

OUTLINE
1.

2.
3. 4. 5. 6. 7. 8. 9. 10. 11.

Introduction Objective and scope of work Literature survey Work plane Material characterizations Compounding of LDPE/PVA Film blowing Studies on films Conclusions Future work References

INTRODUCTION

PE, PP creates heavy littering problem for society Mixing of PVA with these polyolefin's resulting biodegradable PVA has excellent film forming, emulsi-fying and adhesive properties. PVA is an atactic polymeric material but exhibits crystallinity as hydroxyl groups are small enough to fit into lattice.

Why LDPE and PVA

Reasons for LDPE Least cost among all other polymer used for packaging film. Good clarity. It is quite flexible, and tough. Excellent resistance (no attack) to dilute and concentrated acid, alcohols, bases and esters. Good resistance (minor attack) to aldehydes, ketones and vegetable oils.

Reasons for PVA Poly vinyl alcohol (PVA) is a synthetic bio-degradable polymer. PVA has the excellent gas barrier property. PVA combines high tensile strength with ease of film formation and show excellent adhesive and bonding characteristics. LDPE is good material for food packaging but does not have good gas barrier property.

Advantages

Disadvantages
1.

Good gas barrier property of LDPE/PVA blend film. Bio-degradable and disposable film. Good heat seal-ability and adhesiveness.

2.

Manufacturing of PVA blend film is difficult because melting temperature and decomposition temperature of PVA is close. High hydrophilicity of PVA blend film is another problem.

Use levels of Poly vinyl alcohol

Food Category Proposed Food Use Use level of PVA Dairy based desert Ice-cream frozen yogurt 0.2

Confectionery

Multi-component chocolate Bars Ready to eat breakfast cereals with dried fruits Food supplement tablets

1.5

Cereals and cereal products

0.5

Food supplements

0.8

Ready to eat savouries

Nut and fruit mixtures

0.5

Objective

To develop and analyze LDPE/PVA blends films for producing best barrier property at low cost for food packaging applications.

Scope of work in food packaging

PVA has use in the food industries as a binding and coating agent especially in applications where moisture barrier/ protection properties are required. Polyvinyl alcohol is coating agent to tablets and capsules. Confectionery products may also contain PVA in order to preserve the integrity of the moisture sensitive constituents.

Literature Survey
Serial No.
1

Titles and authors name

Oxygen barrier properties of biaxially oriented polypropylene/polyvinyl alcohol blend lms, Jyongsik jang et al Water resistance, mechanical properties and biodegradability of methylated corn starch/poly(vinyl alcohol) blend lm, Zhao Guohua et al Study and development of LDPE/starch partially biodegradable compounds, Nakamura et al

Key points from selected papers

Oxygen permeability of PP/PVA blend film is dependent on the number and size of PVA platelet. Mechanical property of MCS/PVA blend film increases because of compatibility between this blend.

The increase of starch amount in LDPE is responsible for decrease in Mechanical property.

Plan of work
Characterization of LDPE and PVA using MFI, DSC and TGA techniques. Thermal characterization of LDPE/PVA blends using (DSC,TGA,MFI, Capillary Rheometry) techniques. Morphological characterization (SEM,XRD) Evaluation of LDPE/PVA blend films characteristics Barrier properties, Mechanical properties, Optical Microscopy

EXPERIMENTAL

Raw Materials and Characterization

Reliance grade 24FS040 LDPE Poly vinyl alcohol (PVA) 99% hydrolyzed having molecular weight 70,000 from SigmaAldrich.

Melt Flow Index

MFI value of LDPE sample was measured at a temperature of 190C and 2.16 kg load ,for per 10 min. MFI result = 3.53 g/10 min.

Differential Scanning Calorimetry

FOR LDPE
Crystalline temp. Tc =97.5C Melting temp. Tm =111C

FOR PVA
From 1 st heating Melting temp. Tm=220.4C Glass Transition temp.= 89.5C From 2 nd heating Melting temp. Tm=214C Crystalline temp.=173.4C Glass Transition temp.= 73.5C

Thermo gravimetric analysis(TGA)

The TGA results shows that thermal decomposition of PVA occurs in two phase at 287.9 C with 71% wt. loss and at 449.4 C with 17% wt. loss. A very sharp decomposition peak for LDPE at 480.7 C with 99.8% wt. loss.

Blending operation
LDPE
Low cost High barrier property

PVA

LDPE/PVA Blend
Moderately low cost with good barrier property

Formulations of Compounding
Serial No. 1 2 3 4 5 LDPE (%) 100 99.5 98.5 97 95 PVA(%) 0 0.5 1.5 3 5

Compounding was done in Prism Eurolab twin screw co-rotating extruder with following parameters: rpm = 250

Die Zone

Zone 8

Zone 7

Zone 6

Zone 5

Zone 4

Zone 3

Zone 2

Zone 1

Feed Zone

230C

225C

225C

220C

215C

210C

210C

207C

205C

205C

Thermal characterizations of LDPE/PVA blends

DSC results
Sample DSC results
PVA (PURE) LDPE (100) LD-PVA (0.5) LD-PVA (1.5)

Tc (C)
173.3 97.5 97.7 97.8

T(melt)
214.0 111.0 110.8 110.6

Melting Enthalpy (j/g)

63.1 148.7 144.7 140.3

Crystallinity (%)
42.1 50.7 48.6 48.5

LD-PVA (3)
LD-PVA (5)

97.7
97.8

110.7
110.7

138.0
133.4

47.9
42.1

From above results there are negligible changes in crystalline temp. and melting temp., slightly changes in melting enthalpy but crystallinity of LDPE decreases with increase of PVA percentage may be because of the disturbance of linear chain arrangement of LDPE.

TGA results
Sample
LDPE (100)

T onset (C)
460.8

Tmax (C)
480.7

% wt. loss
99.8

LD-PVA (0.5)

454.7

481.4

99.6

LD-PVA (1.5)

458.1

481.0

99.6

LD-PVA (3)

457.2

481.6

100.0

LD-PVA (5)

457.6

480.3

97.7

With increase in percentage of PVA in base LDPE matrix there is negligible changes in degradation onset temp. and % weight loss of LDPE/PVA blends.

MFI results
The MFI value calculated at 230C temp.,2.16 kg load for per 10 minutes
Samples LDPE LD-PVA (0.5) LD-PVA (1.5) LD-PVA (3) LD-PVA (5) MFI (gm/10 min.) 9.85 9.53 9.32 9.31 9.29

MFI values of all LDPE blends are decreases. This result can be predicted that the chemical bonding between LDPE/PVA increased with increasing amount of PVA, resultant decrease in MFI value reported.

Rheological measurement of LDPE/PVA blends by Capillary Rheometry:

300

The Power Law model is a model that is ideal for shear thinning.
250

Shear Viscosity (Pa.S)

200

150

LDPE LD-PVA LD-PVA LD-PVA LD-PVA

= K n-1
0.5 1.5 3 5

Where = viscosity = shear rate K= consistency

100

50

500

1000

1500

2000

2500

3000

3500

4000

Shear rate (/s)

Power Law Index

0.9 0.8

Power Law Index (n)

0.7

0.6

0.5

0.4 0 1 2 3 4 5

PVA (%)

Fig. Power law index against PVA % In the above graph power law index value (n) of LDPE/PVA blends continuously increasing , which is in the range of shear thinning 0<n<1. So viscosity of blends also gradually increasing and moving towards shear thickening.

Blown film processing of LDPE/PVA blends

Blown film of LDPE/PVA blends were prepared in Haake blown film processing unit on following parameters Temperature profile: 230C rpm: 30

Evaluation of LDPE/PVA Blends film characteristics

Mechanical properties of films in machine direction

Sample Tensile Modulus (MPa) LDPE (100) 239.85 Tensile Strength (MPa) 12.51 % Elongation at break 91.31

LD-PVA (0.5)

250.10

16.75

256.49

LD-PVA (1.5)

295.17

22.87

203.26

LD-PVA (3)

302.48

21.98

264.09

LD-PVA (5)

279.14

20.22

157.50

Fig.1: Tensile Strength Vs PVA %

Fig.2: Tensile Modulus Vs PVA %

24

310 300

22

290
20

18

Tensile Modulus
0 1 2 3 4 5

Tensile Strength

280 270 260 250 240

16

14

12

230 0 1 2 3 4 5

PVA %

PVA %

From above results it is concluded that in all LDPE blend samples tensile modulus, tensile strength and % elongation at break values are higher as compare to neat LDPE. So it can be concluded that PVA reinforced the LDPE matrix.

XRD graphs of LDPE/PVA blend films

8000 7000 6000 5000 4000 3000 2000 1000 0 10000 8000 6000 4000 2000 0 7000 6000 5000 4000 3000 2000 1000 0 10000 8000 6000 4000 2000 0 12000 10000 8000 6000 4000 2000 0 0 10 20

LD-PVA 5

LD-PVA 3

Intensity

LD-PVA 1.5

LD-PVA 0.5

LDPE

30

40

50

2 Theta(degree)

XRD results of LDPE/PVA blown film

Samples LDPE (100) Crystallinity (%) 53.9

LD-PVA (0.5)
LD-PVA (1.5) LD-PVA (3) LD-PVA (5)

52.8
47.6 45.9 41.3

Above table of XRD results shows that crystallinity of LDPE blends are gradually decreases with increase PVA percentage, which is also satisfy by DSC results.

Conclusions

Tensile strength of blend films increases with increase in PVA percentage. Viscosity of blend films are increases so barrier property should be increase. LDPE/PVA blend films may be the good alternative to replacement of PVDC coated BOPP film used for food packaging applications.

Future work
Barrier property studies on LDPE/PVA blend films Use of LDPE-g-MA compatibilizer with LDPE/PVA blends Film blowing of LDPE/PVA blends with LDPE-g-MA Use of nano clay in LDPE/PVA composition to study on barrier property.

References
[1] Jyongsik Jang, Dong Kweon Lee, Oxygen barrier properties of biaxially oriented polypropylene/polyvinyl alcohol blend lms, Polymer, Volume 45, Issue 5, March 2004, Pages 1599-1607 . [2] Jyongsik Jang Dong Kweon Lee, Plasticizer effect on the melting and crystallization behavior of polyvinyl alcohol , Polymer, Volume 44, Issue 26, December 2003, Pages 81398146 . [3] E.M. Nakamura, L. Cordi, G.S.G. Almeida, N. Duran and L.H.I. Mei , Study and development of LDPE/starch partially biodegradable compounds, Journal of Materials Processing Technology, Volumes 162-163, 15 May 2005, Pages 236-241 [4] Chi-Yuan Huang, Ming-Lih Roan, Mei-Chuan Kuo, and Wan-Ling Lu, Effect of compatibiliser on the biodegradation and mechanical properties of high-content starch/lowdensity polyethylene blends, Polymer Degradation and Stability, Volume 90, Issue 1, October 2005, Pages 95-105 [5] Zhao Guohua, Liu Ya, Fang Cuilan, Zhang Min, Zhou Caiqiong, Chen Zongdao, Water resistance, mechanical properties and biodegradability of methylated-cornstarch/poly(vinyl alcohol) blend film Polymer Degradation and Stability, Volume 91, Issue 4, April 2006, Pages 703-711. [6] Thas M.C. Maria, Rosemary A. de Carvalho Paulo J.A. Sobral, Ana Mnica B.Q. Habitante and Javier Solorza-Feria, The effect of the degree of hydrolysis of the PVA and the plasticizer concentration on the color, opacity, and thermal and mechanical properties of film based on PVA and gelatin blends , Journal of Food Engineering, Volume 87, Issue 2, July 2008, Pages 191-199.

THANK YOU

APPENDIX