enhancing performance of liquid packaging - aimcal · enhancing performance of liquid packaging ......

Easy Pour and Improved Evacuation: Enhancing Performance of Liquid Packaging

Kent O’NeillKent.o’[email protected]

October 12, 2016

A World Leader, Focused on Innovative Solutions to Meet Our Customers’ Needs

2

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27 countries• 4,900 employees• More than 800,000 metric tons of annual

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% of Revenue

Outline

• Background– Surface energy / Solid-Liquid Interface / Contact Angle– Surfactants– Food product characteristics

• Methods/Materials/Experimental data– Materials: Food products, Film structures / surfaces– Methods– Experimental Data

• Conclusions / Future Work

3

Section One

4

Background

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Stand-up pouches for liquid products

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• “Stand-up pouches projected to grow by 7% each year through 2018”

• Movement away from rigid packaging to stand-up pouches driven by several factors, such as:

Reduced plastic use (~60% lower) Lower landfill waste Lighter Portability

....

Ref: packagingstrategies.com

Challenges Facing Packaging of Liquid Products

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More viscous liquids can stick to the walls of the package • Slows dispensing• More effort by consumer and sometimes messier

Incomplete evacuation can result in product waste

Liquid Behavior

7MIT Introduction to Surface TensionSurface Tension and Surface Energy. Eyland.com.auGraphic: Difference Between Surface Tension & Surface Energy. Pediaa.Com

In the bulk, molecules are uniformly surrounded and forces balanced

Molecules at the surface missing some attractive interactions

Energy state is unfavorable and causes inward cohesive force

Shape is changed to expose smallest surface area Liquid surface under tension due to imbalance

(=surface tension; force per unit length)

Surface Energy

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• Specific surface energy of a material is the excess energy per unit area due to the existence of the free energy at the surface

• γ = specific free energy (mJ/m2)

• Water = 73• Olive oil = 32• PE = ~35

Ref MIT surface tension of polymers,Chemistry of materials, April 2015 – Surface tension values

Solid-Liquid Interfaces and Contact Angle

9

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• When a liquid drop is placed on a surface, it adopts a minimum free energy state, resulting in a contact angle.

• The contact angle is the measurement of the energy of interaction between a liquid and a solid

• Can provide estimate of polar and non-polar interactions at interface

Ref SpecialChem contact angle webinar

Liquid

Wettability

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Wettability refers to how a liquid spreads out when dropped on a solid surface

Liquid

Solid

Non-wetting

High Contact Anglebetween 90 – 180°

Solid

Wetting

Low Contact Angle< 90°

Contact Angle

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• Hydrophilic – H2O contact angle < 90°

• Hydrophobic – H2O contact angle > 90°

• Oleopophilic – oil contact angle < 90°

• Oleophobic – oil contact angle > 90°

Ref journal of material science 2011 46:69-76, image wikipedia

Typically measured with water but can also be conducted with other fluids (e.g. oil)

Can provide estimation of surface functionality

Altering Polyolefin Surfaces

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• Polyolefins (e.g. PE, PP) are non-polar

• Surface Energies ~ 30-35 mJ/m2

• Contact Angle ~ 89°

• Use of surface active agents (surfactants) which can alter the surface energy and contact angle

Surfactants

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• Surfactants are amphiphilic molecules with a polar head and a non polar tail

• In polymers, majority are migratory (but there are some polymeric additives which don’t migrate)

Source image – University of Bristol

• The main factors that influence migration Crystallinity of polymer Level of unsaturation of surfactant Chain length

Surfactant Behavior at Polymer Surface

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Depending on the chemistry

Polymer

• Surfactant aligns in head to head configuration

• non-polar surface

• Surfactant aligns with head projecting

• polar surface

Food Products – Some Classifications

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Rheological Behaviors

• Newtonian – constant viscosity independent of applied forceExample: Olive oil

• Non-Newtonian – viscosity changes when force appliedExample: Ketchup

• Low to high viscosity

Example Types

• Aqueous• Dairy products and modifications –

Water-in-oil or oil-in-water emulsions (High or Low Fat)

• Low-moisture fats and oil

In accordance with 21 CFR 176.170 (c) Table 1 Food Rheology. Karwe. Rutgers University.

Section Two

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Materials, Methods, Experimental Data

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Food Products in Study: High Viscosity

17Ref Syokuhin food products viscosity chartImage Source - Alimenco

For our study:

Food substances with viscosities in the ~104-105 mPa∙s (cp) or greater range

• Tomato Paste – 104-105

• Peanut Butter – 104.5-105.5

• Mayonnaise - 103.5-105

Food Products in Study – Medium Viscosity

18Ref Syokuhin food products viscosity chartImage source - itsybitsyfoodies

Food substances with viscosities in the ~103-104 mPa∙s (cp) range

• Ketchup – 102.7-104

• Ranch – 104

Food Products in Study – Low Viscosity

19Ref Syokuhin food products viscosity chartImage Source – Kenwood world

Food substances with viscosities < 103 mPa∙s (cp)

• Tomato Sauce – 102.5-103.5

• Pasta Sauce – ~103

• Pizza Sauce – ~103

Classification by Type – Aqueous Products

20Ref Food ingredient label

Based off of majority component

• Tomato Paste – Tomato Paste (Hunts)

• Tomato Sauce – Tomato paste, water (Hunts)

• Pizza Sauce- Water, tomato paste, sugar (Mid’s)

• Ketchup – Tomato concentrate, distilled vinegar, high fructose corn syrup (Heinz)

Classification by Type - Oil Based Products

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• Based off of majority component

• Mayo – soybean oil, water, whole eggs and yolks (Hellmans)

• Peanut Butter – Peanuts, sugar, molasses (JIF)

Ref Food ingredient labelImage source - Igoscience

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• Ranch – vegetable oil, water, egg yolk (Hidden Valley)

Ref Food ingredient labelImage source – www.reference.com

Classification by Type - Similar Water/Oil Ratio Products

Food Products Compositional Information

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Ref. USDA National Nutrient Database

Product Water (g) Total lipid (fat) g Water/Lipid Lipid/Water

Tomato Paste (canned) 73.5 0.47 156X

Tomato Sauce (canned) 91.28 0.30 304X

Ketchup 68.51 0.1 685X

Pizza Sauce, canned, ready-to-serve 86.71 1.15 75X

Pasta sauce / marinara ready to serve 87.87 1.61 55X

Ranch Dressing, regular 45.68 44.54 1X 1X

Mayonnaise, regular 21.65 74.85 3.5X

Peanut Butter 1.23 51.36 42X

Pouch Construction

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Outside

Food contact surface

PET

PE

PE

TIEAl

PE Sealant Film General Structure

25

2 mil Blown film

Outside 33% Exceed 1018 HA +/- Surfactant MBCore 34% 60% Exceed 1018 HA

40% LDPEInside 33% 98% LDPE + 2% F20

Sealant layer exposed to food substances

Films and Masterbatches

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Film ID MB % Active in Skin Layer

Estimated Surface Characteristic

M1402-F1V1

1

Hydrophobic Oleophilic

M1402-F2 2

M1402-F3V2

1

M1402-F4 2

M1402-F5V3

1

M1402-F6 2

M1402-F9V4

1Hydrophilic Oleophilic

M1402-F10 2

M1402-F11V5

1Hydrophobic Oleophilic

M1402-F12 2

Test Set Up – Tilt Test

1. Film mounted flat on a clipboard

2. Substance measured to a specific amount and placed above the start line

3. Clipboard tilted by 45° or 90°

4. Measured parameters:a. Time to cross finish line ORb. Distance travelled in a specific

time

c. Product residue above finish line

Start

Finish

43

Example - Peanut Butter

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• ~4 grams of creamy peanut butter.

• Distance of 30mm.

Leveled off cutlery spoon for measurement

Cutlery knife for application

Placement of substance

Experimental procedure

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• The clipboard is then inverted to ~90° and a calibrated stop watch is used to capture the time it takes for the bottom of the food service to cross the second, or “Final”, line.

“FINAL”

30

149

35 35

24 2636

26

130

8678

62

0

20

40

60

80

100

120

140

160

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Peanut Butter

84%

F0 = Blank ControlDistance = 30 mm

Peanut Butter Evaluation / High Fat to Water Ratio

Mayonnaise Evaluation / High Fat to Water Ratio

31

30.42

239.6

208186.9

132.9145.12

283.2

34.6517.54

71.353.85

0

50

100

150

200

250

300

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Mayo

42%


32

48.4 48.94

28.1

17.59

22.85

27.6223.33

33.61 35.21

23.8120.08

0

10

20

30

40

50

60

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Ranch

64%

Ranch Dressing Evaluation / Equivalent Fat to Water Ratio


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103.55

80.3575.83

118.95

84

94.686.8

37.92

26.77

60.63 57.96

0

20

40

60

80

100

120

140

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Tomato paste

74%


Tomato Paste Evaluation / High Water to Fat Ratio

Ketchup Evaluation / High Water to Fat Ratio

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15

11

7 76

10

12

7

5

98

0

2

4

6

8

10

12

14

16

18

20

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Ketchup67%


Pizza Sauce Evaluation / High Water to Fat Ratio

35

27

21

9

6 6

10

78

7

32

0

5

10

15

20

25

30

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Pizza sauce 93%


Pasta Sauce Evaluation / High Water to Fat Ratio

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4.1

2.53

3.873.65

4.84

3.06 2.89

4.03

2.81

3.97

2.5

0

1

2

3

4

5

6

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Pasta sauce

39%


Tomato Sauce Evaluation / High Water to Fat Ratio

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7.67

6.03

7.12

4.51

3.37 3.53

1.84

5.06 4.78 4.5

7.22

0

1

2

3

4

5

6

7

8

9

10

F0 F1 F2 F3 F4 F5 F6 F9 F10 F11 F12

Tim

e (s

ec)

Tomato sauce76%


Contact Angle Measurement

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Contact angle meter

• Apply droplet of DI water or Olive oil on surface of film.

• Contact angle is read off the projection of the shadow of the water droplet.

• ½ angle method

Contact Angle of Films

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Film IDContact Angle

H2O Oil (olive oil)

F0 (Blank Control) 89° 18°

F1 104° 48°

F2 104° 52°

F3 104° 54°

F4 104° 46°

F5 106° 58°

F6 107° 54°

F9 4° 24°

F10 4° 20°

F11 98° 16°

F12 106° 19°

Hydrophobic and Oleophilic (Higher OCA)

Hydrophilic and Oleophilic (Lower OCA)

Hydrophobic and Oleophilic (Lower OCA)

Water/Oil Contact Angle of Films

40

0

10

20

30

40

50

60

0 10 20 30 40 50 60 70 80 90 100 110 120

Oil

Cont

act A

ngle

Water Contact Angle

HydrophobicHydrophilic

LowerOCA

HigherOCA

Relationship Investigation

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Sample Tilt Test Result

Control Film (F0) Tilt Test Result

• Analysis of data to investigate any trends between surface characteristics versus food type

• Calculate Relationship Factor for Each Sample

• Plot Specimen Relationship Factor vs Water and Oil Contact Angles

• Relationship Factors < 1 = Performance Improvement over Control

Peanut Butter Results vs Surface Behavior

42

0

0.2

0.4

0.6

0.8

1

1.2

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control

Hydrophobic & Higher OCA

Hydrophilic & Low OCA

Hydrophobic & Low OCA0

0.2

0.4

0.6

0.8

1

1.2

0 20 40 60 80Contact Angle

Oil Contact Angle

Mayonnaise Results vs Surface Behavior

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0

1

2

3

4

5

6

7

8

9

10

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control


Hydrophilic & Lower OCA

Hydrophobic & Low OCA

0

1

2

3

4

5

6

7

8

9

10


Oil Contact Angle

Ranch Dressing Results vs Surface Behavior

44

0

0.2

0.4

0.6

0.8

1

1.2

0 50 100 150

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0

0.2

0.4

0.6

0.8

1

1.2

0 20 40 60 80Fa

ctor

Contact Angle

Oil Contact Angle

Tomato Paste Results vs Surface Behavior

45

0

0.2

0.4

0.6

0.8

1

1.2

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0

0.2

0.4

0.6

0.8

1

1.2


Oil Contact Angle

Ketchup Results vs Surface Behavior

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0

0.2

0.4

0.6

0.8

1

1.2

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0.2

0.4

0.6

0.8

1

1.2


Oil Contact Angle

Pizza Sauce Results vs Surface Behavior

47

0

0.2

0.4

0.6

0.8

1

1.2

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0

0.2

0.4

0.6

0.8

1

1.2


Oil Contact Angle

Pasta Sauce Results vs Surface Behavior

48

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0

0.2

0.4

0.6

0.8

1

1.2

1.4


Oil Contact Angle

Tomato Sauce Results vs Surface Behavior

49

0

0.2

0.4

0.6

0.8

1

1.2

0 25 50 75 100 125

Rela

tions

hip

Fact

or

Contact Angle

Water Contact Angle

Control




0.2

0.4

0.6

0.8

1

1.2


Oil Contact Angle

50

High viscosity

Medium viscosity

Low viscosity

Lipid WaterHydrophobic / high oil CA

Hydrophobic / low oil CA

Hydrophilic / low oil CA

42 3.5 1 30475 156 68555*not to scale Lipid/water Water/lipid

Peanut Butter Mayo

Ranch

Pasta Sauce

Pizza Sauce

Tomato Paste

Tomato Sauce

Ketchup

Outcomes of Similar Products

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Water/ Lipid Ratio

Viscosity Best Next Best

Ketchup 685X M F10: Hydrophilic, Low OCA F4: Hydrophobic, High OCA

Tomato Sauce (canned) 304X L F6: Hydrophobic, High OCA F4: Hydrophobic; High OCA

Tomato Paste (canned) 156X H F10: Hydrophilic, Low OCA F9: Hydrophilic, Low OCA

Water/ Lipid Ratio

Viscosity Best Next Best

Pizza Sauce, canned, ready-to-serve

75X L F12: Hydrophobic, Low OCA F11: Hydrophobic, Low OCA

Pasta sauce / marinara ready to serve

55X L F12: Hydrophobic, Low OCA F1: Hydrophobic, High OCA

Section Three

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Conclusions and Future Work

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Conclusions

• A test method has been developed to assess product flow over a film surface; and a small subset of food substances were characterized using this technique

• The surface character of a polymer film can be modified through the use of select surfactants creating water contact angles ranging from 4 to 107° and oil contact angles ranging from 16 to 58°

• No clear trend is visible correlating either product viscosity or composition to a particular surface functionality

• By modification of the polymer surface functionality, the flow of all food products evaluated was increased, with improvements ranging between 39 to 93%.

• This benefit could enable improved pouring / dispensing and reduced residual waste of food products with a range of viscosities in flexible packaging applications

Future work

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• Create Residue test

• Test additional substances to continue to search for trends

• Develop a pouch method

55

• A. Schulman Inc.

• Kari MacInnis – Technical Manager Masterbatch Solutions USCAN

• Kasia Gadomska – R&D EngineerMasterbatch SolutionsEMEA

Acknowledgements

Thank You

Disclaimer

The user is not entitled to copy or distribute this document. You may not copy this document to a Web site. A. Schulman does not guarantee the typical (or other) values. Analysis may be performed on representative samples and not the actual product shipped. The information in this document relates only to the named product or materials when not in combination with any other product or materials. We based the information on data believed to be reliable on the date compiled, but we do not represent, warrant, or otherwise guarantee, expressly or impliedly, the merchantability, fitness for a particular purpose, suitability, accuracy, reliability, or completeness of this information or the products, materials, or processes described. The user is solely responsible for all determinations regarding any use of material or product and any process in its territories of interest. We expressly disclaim liability for any loss, damage, or injury directly or indirectly suffered or incurred as a result of or related to anyone using or relying on any of the information in this document. There is no endorsement of any product or process, and we expressly disclaim any contrary implication. The terms, “we”, “our”, "Schulman Plastics" or “Schulman” are used for convenience, and may include any one or more of A. Schulman Companies, A. Schulman Plastics Corporation, or any affiliates they directly or indirectly steward. Schulman Plastics, the Schulman Plastics Emblem and Polybatch, Polywhite, Polyblak, and Papermatch are trademarks of A. Schulman.

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Confidential

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