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Easy Pour and Improved Evacuation: Enhancing Performance of Liquid Packaging
Kent O’NeillKent.o’neill@aschulman.com
October 12, 2016
A World Leader, Focused on Innovative Solutions to Meet Our Customers’ Needs
2
• Founded 1928 in Akron, Ohio• Expanding footprint with 57 manufacturing sites in
27 countries• 4,900 employees• More than 800,000 metric tons of annual
manufacturing capacity• ~$2.5 billion net sales in 2015
Global Headquarters in Akron, Ohio
% 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
Confidential
Stand-up pouches for liquid products
5
• “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
6
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
8
• 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
Confidential
• 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
10
Confidential
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
11
• 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
12
• 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
13
• 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
14
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
15
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
16
Materials, Methods, Experimental Data
Confidential
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
21
• 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
22
• 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
23
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
24
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
26
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
28
• ~4 grams of creamy peanut butter.
• Distance of 30mm.
Leveled off cutlery spoon for measurement
Cutlery knife for application
Placement of substance
Experimental procedure
29
• 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%
F0 = Blank ControlDistance = 60 mm
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
F0 = Blank ControlDistance = 60 mm
33
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%
F0 = Blank ControlDistance = 30 mm
Tomato Paste Evaluation / High Water to Fat Ratio
Ketchup Evaluation / High Water to Fat Ratio
34
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%
F0 = Blank ControlDistance = 60 mm
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%
F0 = Blank ControlDistance = 60 mm
Pasta Sauce Evaluation / High Water to Fat Ratio
36
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%
F0 = Blank ControlDistance = 60 mm
Tomato Sauce Evaluation / High Water to Fat Ratio
37
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%
F0 = Blank ControlDistance = 60 mm
Contact Angle Measurement
38
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
39
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
41
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
43
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
Hydrophobic & Higher OCA
Hydrophilic & Lower OCA
Hydrophobic & Low OCA
0
1
2
3
4
5
6
7
8
9
10
0 20 40 60 80Contact Angle
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
Hydrophobic & Higher OCA
Hydrophilic & Low OCA
Hydrophobic & Low OCA
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
Hydrophobic & Higher OCA
Hydrophilic & Low OCA
Hydrophobic & Low OCA
0
0.2
0.4
0.6
0.8
1
1.2
0 20 40 60 80Contact Angle
Oil Contact Angle
Ketchup Results vs Surface Behavior
46
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
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
Hydrophobic & Higher OCA
Hydrophilic & Low OCA
Hydrophobic & Low OCA
0
0.2
0.4
0.6
0.8
1
1.2
0 20 40 60 80Contact Angle
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
Hydrophobic & Higher OCA
Hydrophilic & Low OCA
Hydrophobic & Low OCA
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 20 40 60 80Contact Angle
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
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
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
51
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
52
Conclusions and Future Work
Confidential
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
54
• 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.
56
Confidential
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