Beer Aromas: Where They Come From, Whey They Go Packaging Perspective Packaging Material Properties that Effect Beer Aroma &Flavor Stability George K. Crochiere Crochiere & Associates, LLC 4/19/212 Crochiere & Associates, LLC 1 4/19/212 Crochiere & Associates, LLC 2 Aroma & Gasket Interactions Beer Aroma Issue & Packaging Property Beer Aroma Issue Packaging Property Scalping Oxygen Staling & Oxidation Oxygen control, barrier & scavenger Extraction Flavor & Aroma Scalping Gasket chemistry and polarity Contamination from packaging Gasket and coating formulations and sources of materials Contamination from the environment Gasket barrier properties 4/19/212 Crochiere & Associates, LLC 3 4/19/212 Crochiere & Associates, LLC 4 Points for Discussion Oxygen control Aroma & Flavor Scalping Packaging contamination Environmental Contamination Sensory evaluation Oxygen Control 4/19/212 Crochiere & Associates, LLC 5 4/19/212 Crochiere & Associates, LLC 6
Total Package Oxygen (ppb) Total Package Oxygen (ppb) Staling and Oxidation Requirements & Prevention Estimated Quantity of Oxygen in Beer Bottles per Source Requirement Source Prevention Operation Poor Oxygen Control Good Oxygen Control Fuel or reagent Beer Optimize formulation and process to improve masking and resistance to oxidation Oxygen Initial Optimize transfer, filling and sealing process Ingress Package selection Energy Heat Refrigeration Tanks and Transfers 1 ppb 25 ppb Bottling 15 ppb 25 ppb Closing 25 ppb 5 ppb Closure ingress over 4 months* 7 ppb Refrigeration 6 ppb Slows reaction & ingress Light Tinted bottles, sealed boxes Total after 4 months 12 ppb 16 ppb *Area with largest potential for improvement 4/19/212 Crochiere & Associates, LLC 7 4/19/212 Crochiere & Associates, LLC 8 Oxygen Ingress Determination Most polymers barrier properties suffer as heat and humidity increase Many oxygen scavengers are activated by heat and humidity Packages have to be tested filled with non-reactive liquid (stabilized water) Packages are filled at low and consistent oxygen levels Oxygen in packages measured over time Packages can be stored in various environments or abused Warehouse stacking Drop impact Transportation etc. Oxygen Concentration in Beer 45 4 35 25 2 15 1 5 15 3 45 6 75 9 Days Low Initial Oxygen High Initial Oxygen Scavenger Liner Barrier Liner 4/19/212 Crochiere & Associates, LLC 9 4/19/212 Crochiere & Associates, LLC 1 1 12 9 6 Oxygen Concentration in Water 3 6 9 12 15 18 Days Low Initial Oxygen High Initial Oxygen Scavenger Liner Barrier Liner Oxidized Flavor Fresh Flavor Early barrier = Aluminum disk over cork In shell molder barrier polymers Multi-layer polymers & foil Barrier additives to enhance polymer performance Barrier Materials 4/19/212 Crochiere & Associates, LLC 11 June 1, 21 Crochiere & Associates, LLC ASBC Packaging Seminar
Oxygen Ingress (ppb) Crown Closures Barrier Closures and Sealants Twist-off Crown Also used for pryoff In shell molded Pry-off crown In shell molded Effective at reducing the ingress of oxygen, nitrogen and contaminants Reduces the loss of carbon dioxide Barrier properties dependent on Sealant barrier properties Sealant physical properties Closure design Closing conditions June 1, 21 Crochiere & Associates, LLC ASBC Packaging Seminar 4/19/212 Crochiere & Associates, LLC 14 6 4 2 1 Oxygen Ingress Through Crown Liners TPR/TPE PVC EVA Low butyl blend High butyl blend Oxygen Scavenger Sealants Effective at reducing the ingress of oxygen relative to the standard closure and sealant Oxygen scavenger can be added to the sealant, closure or plastic bottle Performance dependent on the activation of the scavenger and path of oxygen ingress Has potential to reduce oxygen in package Shelf-life of scavenger containing materials is limited 1 2 3 4 Months 4/19/212 Crochiere & Associates, LLC 15 4/19/212 Crochiere & Associates, LLC 16 Oxygen Scavengers Used in Closures Material Iron Catalyzed Available Pros -Fast -Triggered Ascorbate Yes -Controlled speed -FDA GRAS Sulfite Yes -Controlled speed -High process temp. -FDA GRAS Cons -Color -Iron pickup -Color -Odor -Expensive -Bad press for corrosion in crowns moisture activated scavenger particle Oxygen Scavenger Schematic inactive scavenger particle oxygen molecule 4/19/212 Crochiere & Associates, LLC 17 4/19/212 Crochiere & Associates, LLC 18
Total Package Oxygen (ppb Total Package Oxygen (ppm) Oxygen Scavenger Effect in Crown Liners.35.3 Oxygen Ingress Through Commercial Crown Liners, 24 PVC.25 4.2 Solid PVC Foamed PVC 1.15 Foamed PVC 2.1 Barrier pry Scavenger 4-old Scavenger 5-old 2 EVA.5 Scavenger 1 Scavenger 2 Scavenger 3. 1 2 3 4 5 6 7 1 -.5 EVA w/scavenger -.1 PVC w/scavenger 1 2 3 4 Months 4/19/212 Crochiere & Associates, LLC 19 -.15 Days 4/19/212 Crochiere & Associates, LLC 2 Molded Liner Materials Material Pry crown Twist crown Aluminum Plastic PVC * * * * TPR/TPE *? * * EVA * * * LDPE * * * Barrier Materials Butyl * * * Accelerated Flavor Testing for Oxidation Fill at low initial oxygen levels Test oxygen ingress not heat aging Heat aging = long term pasteurization Accelerated oxygen ingress = flavor shelf-life Bottles are placed in pure oxygen atmosphere for approximately 5X acceleration 4/19/212 Crochiere & Associates, LLC 21 4/19/212 Crochiere & Associates, LLC 22 Aroma & Flavor Scalping Absorption of aromas & flavors by the packaging (gasket). Scalping Parameters Chemistry and polarity of the polymers (plastics, rubber, paint) in contact with the beer. Size and polarity of the aromas and flavors Non-polar flavors have been studied greatly for the citrus industry Silicone>LDPE>HDPE>PP>PET>Saran Scalping can be used to remove undesirable aromas and flavors (TCA, TBA, TeCA, ) 4/19/212 Crochiere & Associates, LLC 23 4/19/212 Crochiere & Associates, LLC 24
Scalping Evaluation Scalping of mixed aromas & flavors can be selective based on concentrations, kinetics, thresholds, capacity to scalp, etc. Scalping usually happens quickly (hours, days) Avoid accelerated tests A gasket that is good or bad for one beer may be the opposite for another. Crown gasket materials are mixtures of many ingredients Scalping Reference Effects of flavour absorption on foods and their packaging materials, Remco W.G. van Willige Many others available with an internet search 4/19/212 Crochiere & Associates, LLC 25 4/19/212 Crochiere & Associates, LLC 26 Sources for Migration and Contamination Packaging Contamination Migration of plastic and coating ingredients into the beer Crown gasket or liner Coatings, paints and inks on the crown Plastic bottles From the degradation of the packaging materials Hoses and gaskets in the brewery 4/19/212 Crochiere & Associates, LLC 27 4/19/212 Crochiere & Associates, LLC 28 Packaging Material Change in typical odor and flavor of the plastics Minor additives - antioxidants, heat stabilizers, antistats, process aides Major ingredients lubricants, plasticizers, scavengers Dust collected on the inside surfaces (paint, metal fines, dirt, etc.) Food law compliance does not insure NO contamination nor good flavor properties 4/19/212 Crochiere & Associates, LLC 29 PVC Crown Liner PVC polymer, antioxidants, catalysts, emulsifiers in plastisol resins Plasticizers DOP, DIOP, DIDP, epoxidized soybean oil (ESO) Heat stabilizers Ca & Zn fatty acids, ESO, antioxidants Blowing agents degradation products Kickers Zn soaps, fatty acids Lubricants waxes, fatty acids, oils, etc. Oxygen scavengers degradation products, catalysts Pigments Process aids waxes, soaps, oils, etc. 4/19/212 Crochiere & Associates, LLC 3
Coatings (paints) Resins Plasticizers Crosslinking agents Catalysts Pigments Waxes and slip agents Emulsifiers (in water-borne and organosols) Flow control agents surfactants of all kinds Sources of Packaging Degradation Empty package Excess heat and shear from manufacturing Empty and Filled package Heat and moisture during transportation and warehousing Oxidation and degradation of scavengers UV light exposure 4/19/212 Crochiere & Associates, LLC 31 4/19/212 Crochiere & Associates, LLC 32 Material Degradation Bottles Acetaldehydes, antioxidants Closures/liners Aldehydes, ketones, oxidized fatty acids and plasticizers Oxygen scavengers Water soluble scavengers and byproducts Low molecular weight oxidation products Environmental Contamination Things that are often out of your control. 4/19/212 Crochiere & Associates, LLC 33 4/19/212 Crochiere & Associates, LLC 34 Environmental Oxygen Nitrogen UV TCA Solvents Exhaust fumes Perfumes Etc. Detection & Identification of Appearance Odor Sensory Qualitative analysis Quantitative analysis Spiked or dosed controls Knowledge of packaging materials and chemistry 4/19/212 Crochiere & Associates, LLC 35 4/19/212 Crochiere & Associates, LLC 36
TCA (nanograms/liter) Environmental Contamination Chemical contamination from materials in atmosphere where the bottle is located Relative barrier performance determined by storing filled bottles in concentrated environment Analysis for chemical in beverage by appropriate method (GC, HPLC, SPME, etc) 4 4 3 2 2 1 1 TCA Barrier Properties of Crown Liners 1 Months Sealant A Sealant B Sealant C Sealant D Sealant E 4/19/212 Crochiere & Associates, LLC 37 4/19/212 Crochiere & Associates, LLC 38 UV Ingress or Exposure UV effects on beer already known UV also degrades plastics and additives used in packaging This degradation causes flavor problems European mineral water industry has established the Light Box Test Light Box Test exposes filled bottles to fluorescent or Xinon light for one week Analysis by sensory evaluation Typical contaminants include aldehydes and ketones Unpigmented plastic closures are extremely prone to this problem Packaging Material Realities No package or material is perfect All plastics/polymers are permeable and have extractables, but are they detectable and managable? Temperature and humidity can greatly effect barrier performance The number of potential contaminants is endless PVC or Phthalate-free tells you what the gasket is not. 4/19/212 Crochiere & Associates, LLC 39 4/19/212 Crochiere & Associates, LLC 4 Bottom Line on Packaging Crown Gasket Profiles (Sacmi) No bottle or closure is perfect Be aware of the potential problems Determine properties and thresholds that are critical to your product Evaluate and specify performance properties Sensory performance is the bottom line 4/19/212 Crochiere & Associates, LLC 41 4/19/212 Crochiere & Associates, LLC 42