mam ' ‘ lllllllllllllllllllllllllllllllllllllllllllllllllllllll 31293 00897 5140 This is to certify that the thesis entitled QUANTIFICATION AND CHARACTERIZATION OF ADHESION BETWEEN DOUGH AND PACKAGING MATERIAL presented by SHU-SHIN CHOU has been accepted towards fulfillment of the requirements for Masters degree in Packaging t/j/Z/VC ‘C’ ( /:)[Q ;_ T Major professor Date March '30: 1993 0-7639 MS U is an Affirmative Action/Equal Opportunity Institution LlenAnv ‘ Mlchlgan State University PLACE IN RETURN BOX to remove this checkout from your record. TO AVOID FINES return on or before date due. ‘ DATE DUE DATE DUE DATE DUE ‘33 I? '6" 106: J I f‘ , aj MSU Is An Affirmative ActIorVEquaI Opportunity Institution skimming-mud QUANTIFICATION AND CHARACTERIZATION OF ADHESION BETWEEN DOUGH AND PACKAGING MATERIAL BY SHU-SHIN CHOU A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree MASTER OF SCIENCE School at Packaging 1992 ABSTRACT QUANTIFICATION AND CHARACTERIZATION OF ADHESION BETWEEN DOUGH AND PACKAGING MATERIAL BY SHU-SHIN CHOU Degree of adhesion between dough and contacting surface was studied. A wettability test was performed as a indicator of adhesion, and a modified tensile strength apparatus (Stickiforce Meter) was used to determine adhesion between dough and film. In the phase I study, adhesion between fourteen packaging materials and one flour was studied under different temperatures (23°C and 4°C). To simulate the different potential conditions for film contact with dough, the following yeast conditions were used: dough-proof, and contact with film; and dough contact with film, and proof. Wettability and Stickiforce Meter measurements were highly correlated. Proof-first-yeast dough at 4°C on PET G film formed the most adhesive bonds, and contact-first-yeast dough at 23°C on Teflon film had the least adhesive bonds. Phase II study used three different films (PE, PH, and TEFLON) and three flours (Hi-protein, bread, and pastry). The results indicated that bread flour with no-yeast dough on PE film at 4°C had the highest adhesiveness, and pastry flour with contact-first-yeast dough on Teflon film at 23°C had the lowest adhesive properties. Film type, yeast condition, flour type, and temperature all affected dough stickiness. To my mother, Yi-Ling Chen and my father, Hsing-Ling Chow ACKNOWLEDGMENTS I would like to express my sincere gratitude to Dr. Bruce Harte, my advisor, for his guidance, support, and encouragement. Appreciation and gratitude is expressed to Dr. Christopher Lai for sharing his time and expertise in methods development and interpretation of the results. Appreciation is expressed to Dr. Mary Zabik and Dr. Gary Burgess for their participating on my guidance committee. My thanks are extended to Dr. Gill and Dr. Julian Lee for their help in developing the statistical analyze used in this work. Special thanks are extended to all my Chinese friends, and my fellow graduate students for their friendships, and their assistance which helped to make this study successful. Finally, I would like to express my deepest thanks to Douglas & Athena Warner, my brother-in-law and my sister, Famin & Li-Ling Chou, my brother and sister- in-Iaw for their love and encouragement which helped to make this endeavor enjoyable. Without them, it would not have been possible. iv TABLE OF CONTENTS LIST OF TABLES .................................. viii LIST OF FIGURES .................................. xiii INTRODUCTION ................................... 1 REVIEW OF LITERATURE ................................... 4 Theory of Adhesion ................................... 4 Definitions and classifications ......................... 4 Mechanical Interlocking ........................ 5 Diffusion Theory ............................. 6 Wetting and Surface Tension ......................... 8 Surface Tension and Wettability ................. 15 The Interaction Between Packaging Material and Product .................................. 18 Chemical and Physical Properties of Dough .................. 20 Type of Flour and Formation of Dough ................. 20 Dough Development ......................... 21 Constituent Components of Dough Associated With Functional Preperties ........................ 23 Measurement of Physical/ Functional Properties of Dough ................................. 32 Correlation of Measurement in Stickiness with Food ............. 33 Methods of Measurement in Stickiness ................. 34 MATERIALS AND METHODS ................................. 42 Materials .................................. 42 Flour Samples .................................. 42 Film Samples .................................. 42 Analytical Measurements ................................ 44 Determination of the Initial Flour Moisture Content (IMC) .................................. 44 Determination of the Protein Content .................. 45 Determination of the Water Absorption Properties - Farinograph ............................... 45 Stickiforce Meter Determination ...................... 46 Inclined Plane Determination ........................ 46 Experimental Design .................................. 48 Phase I Study ................................... 48 Treatment Variables ......................... 50 Phase II Study .................................. 51 Dough Preparation .......................... 51 Treatment Variables ......................... 53 Statistics Analysis .................................. 54 Phase I Study ................................... 54 Phase II Study .................................. 55 RESULTS AND DISCUSSION ................................. 56 Phase I Study .................................. 56 Inclined Plane Determination ........................ 56 Stickiforce Meter Determination ...................... 56 Wtforce/thass Results ........................... 62 thass .................................. 62 Wtforce .................................. 71 Phase II Study .................................. 80 Inclined Plane Determination ........................ 80 Protein in Flours ................................. 81 Stickiforce Meter Determination ...................... 81 Wtforce/thass Results ........................... 86 thass .................................. 86 Wtforce ................................. 104 CONCLUSIONS ................................. 1 19 RECOMMENDATIONS ................................. 125 APPENDICES pendix A Calculations for Absorption at 14% Moisture Content Basis ................ 126 Appendix B .... Tukey's Honestly Significant Difference Test of Wtforce and thass Results for Phase I study ....... 127 pendix c ' ' ' ' Tukey’s Honestly Significant Difference Test of Wtforce and thass Results for Phase II Study .......... 138 BIBLIOGRAPHY ................................ 154 vii Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. LIST OF TABLES Film samples used in Wettability and Stickiforce Meter - Phase I study ............................. Film samples used in Wettability and Stickiforce Meter - Phase II study ............................ Wettability of distilled water and 50% ethyl alcohol on different material surface. (Phase I study) ........ The effect of treatment on the weight-mass gain per unit (gm /cm2) determined by stickiforce meter (Phase I study) .................................. The effect of treatment on the weight-force gain per unit (gm/cm?) determined by stickiforce meter (Phase I study) .................................. Ranking of dough stickiness to coding (Phase I study) Analysis of variance for Wtforce values of fourteen different films under different yeast conditions at various temperature ......................... Analysis of variance for thass values of fourteen different films under different yeast conditions at various temperature ......................... Wettability of distilled water and 50% ethyl alcohol on different material surfaces (Phase II study) ....... The percentage protein in pastry, bread, and Hi- protein flours .............................. viii 43 45 57 58 60 61 63 63 81 82 Table 11. The effect of treatment on the Weight-mass gain per unit (gm/cm?) determined by stickiforce meter (Phase II study) ............................ 83 Table 12. The effect of treatment on the Weight-force gain per unit (gm/cmZ) determined by stickiforce meter (Phase II study ............................. 85 Table 13. Analysis of variance for Wtforce values of three different types of flours under three different yeast conditions at various temperature on three different films .............................. 87 Table 14. Analysis of variance for thass values of three different types of flours under three different yeast conditions at various temperature on three different films .............................. 88 Appendix A Calculations for Absorption at 14% Moisture Content Basis ...... 126 Appendix B Table 15. thass mean values of the test materials ........ 127 Table 16. thass mean values of the test materials with proof- first and contact-first yeast dough .............. 128 Table 17. thass mean values of the test materials at room (23°C) and refrigerated (4°C) temperature ........ 129 Table 18. thass mean values of proof-first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature .............................. 130 Table 19. thass mean values of the test materials with proof- first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature .............. 131 Table 20. Wtforce mean values of the test materials ......... 132 Table 21. Wtforce mean values of the test materials with proof- first and contact-first yeast dough .............. 133 Table 22. Table 23. Table 24. Appendix C Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. Table 31. Table 32. Table 33. Wtforce mean values of the test materials at room (23°C) and refrigerated (4°C) temperature ........ 134 Wtforce mean values of proof-first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature .......................... 135 Wtforce mean values of the test materials with proof-first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature . . . . 136 thass mean values of proof-first, contact-first, and no-yeast dough ........................ 138 thass mean values of Hi-protein, bread, and pastry flour ................................. 138 thass mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour ............................... 139 thass mean values of room (23°C) and refrigerated (4°C) with proof-first, contact-first, and no-yeast dough ........................... 139 thass mean values of room (23°C) and refrigerated (4°C) with Hi-protein, bread, and pastry flour ...... 140 thsss mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature .......................... 140 thsss mean values of PE, PET, and TEFLON film . 141 thass mean values of proof-first, contact-first, and no-yeast dough on PE, PET, and TEFLON film . . 141 thass mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film ............. 142 Table 34. Table 35. Table 36. Table 37. Table 38. Table 39. Table 40. Table 41. Table 42. Table 43. Table 44. Table 45. Table 46. Wtrnass mean values of Hi-protein, bread, and pastry flour with proof-first, contact-first, and no—yeast dough on PE, PET, and TEFLON film ..... thass mean values of room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film . . Wtforce mean values of proof-first, contact-first, and no-yeast dough ........................ Wtforce mean values of Hi-protein, bread, and pastry flour Wtforce mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour ............................... Wtforce mean values of room (23°C) and refrigerated (4°C) with proof-first, contact-first, and no-yeast dough ........................... Wtforce mean values of room (23°C) and refrigerated (4°C) with Hi-protein, bread, and pastry flour ...... Wtforce mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature .......................... Wtforce mean values of PE, PET, and TEFLON film . . Wtforce mean values of proof-first, contact-first, and no—yeast dough on PE, PET, and TEFLON film . . Wtforce mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film ............. Wtforce mean values of Hi-protein, bread, and pastry flour with proof-first, contact-first, and no-yeast dough on PE, PET, and TEFLON film ..... Wtforce mean values of room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film . . xi 142 143 144 145 145 146 146 147 147 148 148 149 Table 47. Table 48. Table 49. Table 50. Wtrnass mean values of proof-first, contact-first, and no-yeast dough at room (23°C) and refrigerated (4°C) with PE, PET, and TEFLON film ................ 150 Wtforce mean values of proof-first, contact-first, and no-yeast dough at room (23°C) and refrigerated (4°C) with PE, PET, and TEFLON film ................ 151 thass mean values of Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) with PE, PET, and TEFLON film ................ 152 Wtforce mean values of Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) with PE, PET, and TEFLON film ................ 153 xii Figure 1. Figure 2. Figure 3. Figure 4. Figure 5. Figure 6. Figure 7. Figure 8. Figure 9. Figure 10. Figure 1 1. Figure 12. LIST OF FIGURES Adhesion depends on wetting of the surface ..... Stickiforce Meter ......................... Sliding of a drop of fluid along a tilted plane ..... Flow chart of Phase II study ................ The Wtrnass values of proof-first and contact-first yeast dough on various films ................ Tukey’s HSD test Wtrnass mean values of various types of material with proof-first and contact- first yeast .......................... The thass values of room and refrigerated temperature dough on various films ........... Tukey’s HSD test Wtrnass mean values of various types of material at room temperature and refrigerated temperature ................... The Wtrnass values of proof-first and contact-first yeast dough at room and refrigerated temperature Tukey's HSD test thass mean values of proof-first and contact-first yeast at room and refrigerated temperature .......................... The thsss values of proof-first and contact-first yeast dough at room temperature (23°C) ....... The thass values of proof-first and contact-first yeast dough at refrigerated temperature (4°C) . . . xiii ......... 9 ........ 47 ........ 49 ........ 52 ........ 65 ........ 67 ........ 67 ........ 70 ........ 7O Figure 13. Figure 14. Figure 15. Figure 16. Figure 17. Figure 18. Figure 19. Figure 20. Figure 21. Figure 22. Figure 23. Figure 24. Figure 25. The Wtforce values of proof-first and contact-first yeast dough on various films ........................ 73 Tukey’s HSD test Wtforce mean values of various types of material with proof-first and contact-first yeast ...... 73 The Wtforce values of room and refrigerated temperature dough on various films ................... 77 Tukey‘s HSD test Wtforce mean values of various types of material at room and refrigerated temperature ..... 77 The Wtforce values of proof-first and contact-first yeast dough at room and refrigerated temperature ........ 78 Tukey’s HSD test Wtforce values of proof-first and contact-first yeast dough at room and refrigerated temperature ........................... 78 The Wtforce values of proof-first and contact-first yeast dough at room temperature (23°C) ............... 79 The Wtforce values of proof-first and contact-first yeast dough at refrigerated temperature (4°C) ........... 79 The thass values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour Tukey's HSD test thass mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread and pastry flour ............................. 91 The thass values of proof-first, contact-first, and no-yeast dough with room and refrigerated temperature Tukey’s HSD test thass mean values of proof-first, contact-first and no-yeast dough at room and refrigerated temperature ........................... 92 The thass values of Hi-protein, bread, and pastry flour dough at room and refrigerated temperature ......... 94 xiv Figure 26. Figure 27. Figure 28. Figure 29. Figure 30. Figure 31. Figure 32. Figure 33. Figure 34. Figure 35. Figure 36. Figure 37. Tukey’s HSD test Wtrnass mean values of Hi-protein, bread, and pastry flour at room and refrigerated temperature The Wtrnass values of Hi-protein, bread, and pastry flour with proof-first, contact-first and no-yeast dough at room (23°C) temperature ............... The thass values of Hi-protein, bread, and pastry flour with proof-first, contact-first and no-yeast dough at refrigerated (4°C) temperature ............ The thass values of proof-first, contact-first, and no—yeast dough on PE, PET, and TEFLON film ....... Tukey’s HSD test thass mean values of proof-first, contact-first, and no—yeast dough on PE, PET, and TEFLON film The thass values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film ............... Tukey’s HSD test thass mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film ............................... The thass value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with proof-first- yeast dough The thass value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with contact- first-yeast dough .............................. The thass value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with no-yeast dough . . . The thass values of room and refrigerated temperature dough on PE, PET, and TEFLON film ................ Tukey’s HSD test thass mean values of room and refrigerated temperature dough with PE, PET, and TEFLON film 95 95 97 100 101 103 Figure 38. Figure 39. Figure 40. Figure 41. Figure 42. Figure 43. Figure 44. Figure 45. Figure 46. Figure 47. Figure 48. Figure 49. Figure 50. The Wtforce values of Hi-protein, bread, and pastry flour with proof-first, contact-first, and no-yeast dough ..... 105 Tukey’s HSD test Wtforce mean values of Hi-protein, bread and pastry flour with proof-first, contact- first, and no—yeast dough .......................... 105 The Wtforce values of proof-first, contact-first, and no-yeast dough at room and refrigerated temperature . . 108 Tukey’s HSD test Wtforce mean values of proof-first, contact-first and no-yeast dough at room and refrigerated temperature .......................... 108 The Wtforce values of Hi-protein, bread, and pastry flour dough at room and refrigerated temperature ........ 109 Tukey’s HSD test Wtforce mean values of Hi-protein, bread, and pastry flour at room and refrigerated temperature ..... 109 The Wtforce values of Hi-protein, bread, and pastry flour with proof-first, contact-first and no-yeast dough at room (23°C) temperature .................. 111 The Wtforce values of Hi-protein, bread, and pastry flour with proof-first, contact-first and no-yeast dough at refrigerated (4°C) temperature ............... 111 The Wtforce values of proof-first, contact—first, and no-yeast dough on PE, PET, and TEFLON film .......... 112 Tukey’s HSD test Wtforce mean values of proof-first, contact-first, and no-yeast dough on PE, PET, and TEFLON film ................................. The Wtforce values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film .................. 114 Tukey’s HSD test Wtforce mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film ..... 114 The Wtforce value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with proof-first- yeast dough Figure 51. Figure 52. Figure 53. Figure 54. The Wtforce value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with contact-first-yeast dough 115 The Wtforce value of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film with no-yeast dough ....... 116 The Wtforce values of room and refrigerated temperature dough on PE, PET, and TEFLON film ................. 118 Tukey’s HSD test Wtforce mean values of room and refrigerated temperature dough on PE, PET, and TEFLON film ................................. 118 xvii CHAPTER 1 INTRODUCTION Adhesiveness or stickiness between the food stuff and the packaging surface is a complex phenomenon. The sticking of food to packaging surface can be desirable or undesirable to both the processor and the consumer. For example, the keeping quality of sausage products is known to be closely related to the degree of adhesion of meats to the casing. 0n the other hand, the adhering of a food product to the contact surface can result in product loss, and in some cases, poor product appearance. Examples are the adhering of sauces to the surface of squeezable bottles and the attaching of pizza cheese to the surface of folding cartons. Lai (1985, 1987) reviewed the adhesion theories and the factors that affect stickiness. The word adhesion is broadly used to describe the sticking together of two materials with or without an intermediate layer. It is an interfacial phenomenon which, in the food-packaging system, generally involves the liquid-solid interface or solid-solid interface. Only a few methods have been used to measure food stickiness. Most procedures use tensile testing 2 instruments. The negative curve obtained during the measurement has been interpreted to be proportional to the work needed to overcome the stickiness. Other stickiness testing devices which use a similar principle are the Struct-O-Graph (Gaines, 1982), Tensile Adhesion Tester (Yokoyama, 1966), and Adhesion Test Balance (Kumar, et al., 1975). Another common procedure employed to measure stickiness involves weighing the material adhered to the contacted surface (Motegi, 1979; Yokoyama, 1966; Taguchi, et al., 1979). The degree of stickiness is correlated to the weight of the product adhered. Though much attention has been given to many of the chemical and physical properties of food products and polymers including adhesion, little is known about the role of the interface in food product-packaging material interaction, in particular adhesion between a foodstuff and packaging material. Lai (1988) demonstrated that different semi-solid foods interacted differently with plastic surfaces. Furthermore, surface properties of plastics are known to vary due to differences in polymer melt, modification by additives, or chemical reactions (Frisch, et al., 1976; Hair, 1967). As the food industry continues to move toward convenience and pre-cooked foods, increasing numbers of food products are processed at centralized locations in large volumes. Gene Hoffman (Williams, 1990), the senior vice 3 president of SuperValu stores, observed that pre-cooked foods have been identified as a major channel through which retailers and wholesalers can get into serious food marketing. Refrigerated foods offer the consumer the greatest potential for convenience and quality. Many of these products are microbiologically sensitive and have short shelf life. Refrigerated dough is one such product (Pomeranz, 1964). It is often presheeted and cut into shape, requiring minimum preparation by the customer. To avoid spoilage of dough, the product must be kept below 40°F. Quality control of ingredients and processing conditions must be rigorously maintained during production to minimize mold, yeast, and bacteria in growth in the dough. Careful consideration must also be given to packaging of the final product. Sticking of dough to the surface of its container can result in the loss of dough, poor product appearance, and customer dissatisfaction. The objectives of this study are: 1. To evaluate a device for determining adhesion between refrigerated dough and the contacting surface. 2. To determine the influence of flour type, yeast condition, and temperature on adhesion between dough nd plastic films. CHAPTER 2 LITERATURE REV I E. 2.1. Theory of Adhesion 2.1.1 Definitions and classifications Adhesion is the phenomenon that results in surfaces being held together by interfacial forces (Bikales, 1971). The force may be mechanical, electrostatic, or due to molecular attraction. Which type of force depends on whether the interfacial forces results from interlocking action, from the attraction of electrical charges, or from valence forces. Adhesion (ASTM D 907-55, 1958), is defined as the attraction between surfaces being held together by valence forces of the same type as those that cause cohesion, while a substance capable of holding materials together by surface attachment could be defined as an adhesive. Eley (1961) stated that in physical chemistry, attraction between a solid surface and a second phase is called adhesion. Electrostatic forces, van der Waals forces, or chemical valence forces may all promote adhesion. The technical process of producing adhesion between two solids is called adhesive bonding. In many situations, this process is irreversible. 5 A brittle adhesive will fracture cohesively on impact loading because the fracture stress is surpassed (Houwink et a1, 1965). A rapidly loaded rubbery adhesive behaves much like a tough plastic. The adherend will tend to break or deform. But, by using an interlayer of metal oxides to form a boundary, the same rubber will break cohesively. In order to form an adhesive joint, the adhesive must move into the bond area and remain there until the bond is complete (Dr. Alfrey, 1948). Therefore, the rheology of polymer systems has a significant role in adhesion. The measurement and understanding of intermolecular forces responsible for adhesion and cohesion is quite important for chemists and engineers whose work involves adhesion. C CK NC A mechanical interlocking of an adhesive with the surface structure of the adherend on a scale which could be easily recognized and discerned is the oldest and most simple theory concerning adhesion (Booth 1990). However, as adhesive technologies began to incorporate more rigid materials with smooth surface, the overall concept of mechanical bonding became inadequate. In recent times the following four broad areas have been used to explain the normal adhesive phenomena: diffusion process, electrostatic interactions, mechanical interlocking, and adsorption or specific interactions. A fifth category, viscous flow and pressure-sensitive adhesive is used in the particular case 6 of pressure-sensitive adhesives. DIEEHSIQH_IEEQBX Voyutskii (1963) initiated work on the diffusion theory of adhesion. Voyutskii's looked at the adhesion of layers of rubbery materials to each other. This lead to 'autohesion', or the process of self adhesion. Autohesion occurs when the macromolecules are mobile. Portions of the long chain molecules interdiffuse if the two polymer surfaces are in close contact at a temperature above the Glass Transition Temperature (Tg). Vasenin's (1965) concept of adhesion was developed in a more quantitative form. He provided formula expressions, although the mathematics were complex, for the force required to separate two polymer surfaces. This force was directly proportional to the rate of separation and to the fourth root of the time that the surfaces were in contact, as well as inversely proportional to the two-thirds root of the molecular weight to express the force of peeling separation. Campion (1975) considered the roll free volume played within the structure of polymers. He correlated autohesion properties with the cross-sectional area of these holes in the structure. A certain amount of free space exists close to the polymer chain because of the geometry of the molecules. As Young (1805) and others have shown, diffusion is a reasonable and useful explanation of adhesion. When 7 the two polymer surfaces are above their Glass Transition Temperature, their molecular chains have same mobility. Derjaguin (1955) and co-workers developed an explanation for some of the properties of pressure-sensitive tape based upon the concept of an electrostatic double layer at the interface. The peeling apart of the adhered surfaces was identified as an electrical capacitance, with the electrical energy stored within. Derjaguin (1969) emphasized that the force of attraction between the plates of a condenser is independent of their distance from each other. Once the process of separation has commenced and the separation of the two parts of a joint increased, the electrostatic force will become much more significant. Mechanical interlocking in structural joints has had a great impotance in the aerospace industry and in the production of motor vehicles. It is phenominal that abrading a surface frequently results in stronger bonds. Abrasion takes away a whole range of materials such as dirt and dust, grease or films of oil, poorly adhering layers of oxide etc., so that a relatively clean surface can be obtained and enables a stronger bond to be occur. Valency forces are usually described as the mechanical strength of any solid material which originates from the various forces of attraction between the ultimate particles (Booth, 1990). Van der Waals' forces are always present no matter which of these forces are significant in any 8 particular material, and their numbers depends upon the chemistry involved. 2.1.2 letting and surface tension Basic to Young's (1805) concept of adhesion is the contact angle 9 between a drop of liquid and a solid surface (Fig 1). The liquid is static when 6 > 0°. At a rate depending on the viscosity and surface roughness, the liquid will wet the solid completely, and then spread freely over the surface. Therefore, contact angle, 6, not only is a good inverse measure of wetting and spreadability, but of adhesion as well. Young (1805) initiated the theory that three surface tensions, stor ySL°, and yLv°, existing at the phase boundaries of a drop of liquid at rest on a solid surface (Fig 1), form a system in static equilibrium. If the molecules that make up the surface are more polar, the surface is easier to wet and bond with a polar liquid adhesive. Consider two glass plates between water for example. The polar groups in the glass plate's surface attract the water molecules and the liquid spreads over the surface. The force of adhesion becomes evident when you try to pull the glass plates apart. Therefore, the essentials for good bond formation would be a liquid adhesive which gives close molecular contact, wets the surfaces to be adhered, and solidifies the liquid between the surfaces. The energy involved in the relationship between a .mooatsmoEB 9.535% 5822 .p 959... W////////////////// was i --// e>m>.. a Q 04w? 5 _ fl . .3... .e 88> 10 liquid and a solid in contact has to be taken into consideration. Young (1805) considered that a drop of liquid on a solid surface is in equilibrium which resulted in the following equation: vsv = 731, + rm (case) (1) Dupre (1869) also expressed the reversible thermodynamic work of adhesion to separate two phases which were originally in contact with each other using the following equation: WA= yl + 72 - 712 (2) where y = surface tension 0 = contact angle conventionally measured through the liquid WA= the work of adhesion In Young's equation, the solid and the liquid were in equilibrium with the vapor, but in Dupre's equation both surfaces were clean and the solid was not in equilibrium with vapor. There is an additional term needed, which is the spreading pressure to express the difference in energy between a clean solid surface in a vacuum and the samesolid surface in equilibrium with the vapor of a liquid. The equation is: WA = VLv (1 + cosO) + n (3) The contact angle indicates the extent a liquid wets and spreads spontaneously on a solid. The liquid will remain a droplet if the temperature is close to 180°F (see figure 1); 11 but will wet and spread on the solid surface if 6 is small. This proves that the smaller the contact angle the better the solid will wet. External pressure can also be applied to the solid to increase the wetting and spreading. The spreading of a liquid over a solid, occurs through the condensation of vapor from the liquid over the solid and the subsequent spreading of the bulk of the liquid over the film of condensed vapor (Burden, 1949). Spreading is the process that involves a reduction in free energy. A solid surface is easily contaminated with foreign matter in a thin layer unless special precautions are taken. When left unprotected in ordinary air even for a short while, a film of greasy material will be detected on a solid surface. Quincke (1859) found that when the surfaces are considerably torn and scratched, sliding becomes impossible unless great force is applied. The ease of wetting is greatly decreased by traces of grease which in turn increase the contact angle against water. Dupre's equation for a solid and a liquid: wsL = st + YLA + YSL (4) where ysA = surface tension of the solid against air surface tension of the solid against liquid 78L surface tension of the liquid YLA Equation (4) shows the relative strengths of the adhesion of the liquid to the solid, and from it can be determined the contact angle. When the liquid attracts the 12 solid as much as it attracts itself or when the liquid attracts the solid more than it attracts itself, the contact angle will be zero, W = ZyLA. When the attraction of the liquid for the solid is half that of itself, the contact angle will be 90°, and when there is no adhesion between the liquid and the solid, the contact angle will be 180°. If two microscopic glass slides are laid on top of each other with a few drops of water in between, it will be very difficult to separate them (Booth 1990). Two kinds of energy must exist in order to separate them. First, the entire thin, liquid layer between the slides must flow into a smaller area to allow for the increased distance which separates them. In order to overcome the viscosity of liquid flowing through a small gap, an expenditure of energy is required. This increases the thickness which in turn increases the surface area around the periphery. Because of the surface free energy of the additional new surface, additional energy will be required. Such a phenomenon exPlains the adhesion of pressure-sensitive tape. The backing is thin and flexible, allowing it to conform closely when it is applied to a surface and pressed down. By coating the backing with a thin film of a viscous liquid, adhesion can occur because the viscous liquid flows across and penetrates the irregular surface when pressure is applied. The ability of the backing to conform and the liQUid to penetrate is dependent upon the pressure applied 13 while applying the tape. In order to obtain proper wetting between two substances, A and B, at least one has to be applied in the liquid or plastic state, or in the highly elastic state (DeBruyne et al, 1951). When volume and temperature are constant, the following equation is true (Houwink, 1965): AF = AU - TAS (5) Where AF = free energy U internal energy S = entropy AF controls the change in internal energy and the change in entropy. In order for wetting to occur, the solvent must be in contact with the molecules of the solid. According to equation (5), as the solid's molecules attract those of the solvent, heat is liberated, if AU is negative, wetting will occur with certainty. When the solvent attracts its own molecules more than the solid's molecules attract those of the solvent, then wetting may or may not occur, depending on the magnitude of (AU - TAS). Equation (6) shows that wetting results when the surface of the solid disappears and the interface appears: Auw = AUS + AUL - AU’SL (6) energy of wetting where Uw US = energy of solid surface UL = energy of liquid surface U51." energy of interface 14 Initially, because of van der Waals forces between the atoms in the two surfaces, the materials adhere to each other. The real strength of the adhering materials is much weaker than the interfacial strengths. The absence of weak boundary layers also brings the two surfaces together. Conventional techniques, such as surface oxidation by corona discharge or flame treatment, are believed to be effective since they create wettable polar surfaces so that the adhesive may spread spontaneously and provide extensive interfacial contact (Bikerman, 1968). The subject of wetting has been dealt with extensively in the literature (Zisman, 1962, 1963, 1964; Good, 1960, 1964). Several studies have been done, but the mechanisms and criteria proposed for establishing relationships between wetting and adhesion have not been consistent. Zisman (1962, 1963, 1964) recognized many of the pertinent relationships which occur with adhesion and discussed them in detail. He did not however establish the importance of these relationships to the problem of adhesion. Sharp, and Schonhorn (1964) emphasised the role spreading has on adhesion and concluded that in order to form a satisfactory adhesive bond, the adhesive must exhibit a surface tension at bonding temperature. Johnson and Dettre (1964) have shown that for most practical coating or adhesive systems, the adhesive will exhibit contact angles with the solid subtrate which are 15 less than 90°, case will be positive, and thermodynamic equilibuium will correspond to a wetted state. Several factors may affect the rate of wetting, the main factor, likely being the viscosity of the liquid adhesive. Another is interfacial topography, which influences the resistance to flow. Yet another, relates the dimensions of the interstices directly to the flow rates in the interfacial interstices. 8 AC N ON W T LITY Surface tension is the measure of the tendency of the boundaries between liquids and gases or between two different liquids to contract (Bikerman 1968). A liquid- liquid interface is often referred to as interfacial tension. For this research, wettability of solid polymers is a far more important property than surface tension of liquid polymers or of polymer solutions. Whether a polymer is suitable for a raincoat, can be printed upon, or has easy gluability depends on its wettability. Contact angle is a quantitative measure of wettability. The following are methods used to measure the contact angle: direct measurement on a drop (Ray et a1, 1985), the drop dimensions (Allan, 1959), angle of sliding (Bikerman, 1950), (Kawasaki, 1960, 1970), and wetting hysteresis (Bikerman, 1958). Different methods are employed, depending on the different kinds of materials and solutions. Fowkes (1952) stated that the basic factor in wetting 16 is the free energy of interaction between the liquid and solid phases across the interface. This free energy is equal to the reversible work of adhesion WA, which is the sum of several kinds of interfacial attractions: WA = WAD + Wm + WBP + w," + WEE (7) where D = dispersion forces H = hydrogen bonds P = other polar interactions n = pi-bonds E = electrostatic interactions The work of adhesion can be quantified as W; = YLv + (st - ySL). This is a useful equation for some supercooled isotropic liquids when their surface free energies are equal to the surface tensions. Interfacial tension is the force which keeps surfaces apart or causes them to coalesce (Young, 1945). However, when contact occurs between a solid or a liquid and a gas, the forces established at the interface are called the surface tension. A substance may react differently in different situations. For example, the effect of water coming in contact with a clean leaf acts differently than when it makes contact with a dusty leaf; cotton sinks in soapy water, etc. These differences are a result of surface active agents. Surface-active agents are compounds which cause variations in either interfacial tension or surface tension. 17 The atomic theory states that all matter consists of atoms and, as a result of recurring constant arrangements of atoms, many familiar molecules are formed. These molecules will have average forces in all directions that are equal and the attraction forces in the interior surface of a mass of the material will be balanced in all directions, and there will be uneven forces at the surface. As the temperature of a liquid increases, the attraction between the molecules decreases. If the temperature increases to the critical point, the surface tension becomes zero. Foreign matter also impacts the adhesive ability of matter. Two drops of clean mercury fuse very readily, but the presence of dust, oil, or other foreign matter on the surface of the mercury will prevent easy union of the two drops. A fundamental factor in wetting is the reduction of surface tension. Given two pure liquids with equal viscosity and volatility, the one with the lower surface tension will spread on a clean glass plate more rapidly. The outer layer of molecules is under contractile tension because of the unbalanced cohesive forces occurring at the surface of a liquid. Accordingly, substances such as fatty acids and alcohols containing both hydrophilic and hydrophobic groups spread out over a large area. Water wets a substance only if the forces of adhesion for the adsorbing surface are stronger than the forces of cohesion between the 18 water molecules. Langmuir (1916), and Harkins et al (1917) stated that absorption takes place because of a surface force presence. Cohesion is the force which holds like molecules together, and the forces of attraction between unlike molecules is adhesion. Langmuir and Harkins also stated that in general, wetting is a chemical phenomena, and the forces related to it are those classed under adsorption. The terms "chemical attraction”, "residual valencies", and "unsatisfied chemical affinities" are also used in connection with adsorption. Bartell (1931) explained that a most common type of adsorption of liquid by solid is wetting by water. Wetting by water may consist of the following three types: (1) spreading wetting (water wets a plain surface); (2) adhesional wetting (water acts as a cementing substance between two or more solids); and (3) immersional wetting (interior capillaries of a porous substance like wheat grains are wetted by water). An example of adhesional wetting by water would be when water assembles the flour particles into the dough mass. 2.1.3 The interaction between packaging material] product Experimental values for adhesive performance are influenced by the gross-sample geometry, the topography of the interface, the chemical nature of the materials, the mechanical responses of the solid and the viscoelastic phases, strains rates, strain geometry, temperature, and 19 such unknowns as the thermodynamic state of the system (Huntsberger 1963). Huntsberger developed the concept that poor performance results from poor interfacial contact. He also established that the way in which the adhesive bonds was formed was greatly influenced by the temperature dependance of the adhesive performance. The effect of different container surfaces on the flow rate of food or beverage is an important attribute in fluid and semi-solid food (Kiosseoglou et a1, 1983). They suggested that the degree of wetting of the surface is an important factor affecting spreadability. Steele (1979) found that bakery products tend to stick to trays. It was caused by the water in dough wetting the metal surface and then drying during baking and the dissolved materials are deposited to form a bond between the metal and the product. He concluded that in order to minimize adhesion of dough to aluminum trays, there should be a high degree of wetting of the aluminum surface with an oil and a low degree of wetting of the oil surface on the tray by the water in the dough. Lebedev et a1 (1975) stated that the surface roughness of the container influences adhesion. He and a co-worker found that adhesion of spaghetti dough to molds was related to the degree of unevenness of the metal surface. Lai (1985) found that different food materials wetted the polymeric film differently. He demonstrated that food 20 interacts differently on plastic surfaces by studying their spreading properties. He also stated that degree of wetting was determined by the spread ratio, coefficient of wetting, and coefficient of traction. 2.2. Chemical and Physical Properties of Dough 2.2.1 Type of flour and formation of dough Wheat flour is a complex system of protein and carbohydrates and is susceptible to various stress conditions (Hlynka, 1964). Wheat is unique among the cereal grains in the type of products which can be produced from it (Hoseney et al, 1978). Wheat flour is the only flour that will produce good quality bread, cakes, cookies or pasta. Although there are many different kinds of wheat grown around the world, they can be categorized into three types generally: (A) The Bread Wheats: These are generally hard wheats and have a somewhat high protein content. (B) The Soft Wheats: The bonding between the protein and starch is weak in this type wheat. This category produces flour with small particle size and has a low level of starch damage during milling. (C) The Pasta Wheats: These are usually hardy wheats such as durum wheats and are preferred for making pasta. One of the most important characteristics of a bread flour is the breadmaking quality (Hoseney et a1, 1978). This quality can be defined in terms of the number of loaves 21 produced by the flour. Loaf volume is one important parameter in judging flour. Although a high loaf volume does not necessarily indicate good flour quality, a poor loaf volume will indicate poor flour quality. The highest loaf volume possible consistent with a good crumb grain is most desirable. UGH ELOPMENT A rubbery mass of wet lumps with little coherence, is obtained during the early mixing of dough ingredients (Pomeranez, 1964). Gradually, the coherence increases, and the dough develops elastic properties and begins to pull away from the mixing bowl which makes the dough more smooth and gives it a drier appearance. This is called dough development. The time needed for optimum development usually varies with the type and speed of the mixer, the type of flour, and the water content of the dough. However, as mixing continues, the dough eventually loss its elasticity, becomes highly extensible and sticky, and in somewhat fluid. This is usually referred to as dough breakdown. Dough could be described as a compound colloid (Swanson, 1943). When we mix flour with water, the protein particles which form gluten unite into filaments or strands, and form a three dimensional network and thus a continuous phase or system. Starch granules are speshed in this network. Water absorbed by the protein particles and starch 22 granules also forms into a continuous phase. Ingredients such as salt, sugar, yeast, and other soluble materials are dissolved in the water solution and their contact with the starch and protein is in the discontinuous phase. Hlynka (1970) suggested that mixing results in unfolding and orientation of long-chain molecules. This leads to a condition of more laminar flow in the dough, which makes the dough less resistant to extension. Hoseney and Finney (1974) speculated that this orientation of protein molecules could increase the probability of hydrogen bonding resulting in a release of water. The increase in free water in dough may be among the factors explaining the lower resistance in overmixed dough to extension as well as its wet and sticky appearance. Dough mixing involves the combining and blending of the formula ingredients. After applying sufficient physical work to the mixture, it will be transformed into a cohesive mass with the requisite viscoelastic properties (Pyler, 1988). The actual proof time will vary depending on the dough's character. Factors such as inadequate yeast content and poor control of time or temperature during fermentation result in extended proof time. During fermentation, proofing and baking, the walls of the dough gas cells are subjected to considerable tensile and shear stress (Pyler, 1988). Therefore, it is necessary for them to possess viscoelastic properties which will allow 23 sufficient expansion and also to sustain these extensions without rupture. From observation on fermenting doughs (Matz, 1960), it was formed that there was a tendency for the starch and gluten to separate during fermentation and for the gluten to form into transparent cells. These transparent cells were drawn to the surface because the gas nucleus from which the bubbles originated is a glutinous core. As the bubbles expand, the required amount of gluten needed to satisfy surface needs is drawn from the starch-gluten matrix of the endosperm material. The properties that enable this to occur may be controlled by the viscosity and fluidity of the gluten and the amount of adhesion of the gluten to starch. Yeast action in fermentation leads to two primary results: (1) The formation and migration of carbon dioxide culminating in a network of cellular compartments to lighten or raise the dough, thereby greatly improving its ultimate palatability; and (2) the simultaneous production and concentration of alcohols, aldehydes, ketones, and acids which contribute to bread aroma and flavor. Yeast also alters the physical properties of dough, especially the gluten elasticity, through the powerful stretChing actions generated by the diffusion and accumulation of carbon dioxide throughout the dough mass. 24 2.2.2 constituent components of dough associated with functional properties According to Parker and Taylor (1966), adhesion can be defined as the use of one material to bond two other materials together, and cohesion as the joining together of the same material (Cherry, 1981). Cooking builds up additional adhesive and cohesive interactions among protein, lipid, and carbohydrate components of foods. Using the scanning electron microscope, Khoo et al (1975) observed that dough consists of starch granules held together by a matrix of hydrated gluten protein. Polar groups contribute greatly to adhesion and cohesion of protein to carbohydrates. The chemistry of adhesion involves nonpolar interactions involving long chain aliphatic or aromatic groups such as Van der Waal or London fores (Parker et al 1966). Disulfide bonds in the amino acid cystine are important to the properties of many proteins by maintaining covalent intramolecular bonds and crosslinks between protein chains (Wall 1971). Complex gluten proteins can be separated, by measuring differences in solubility, which leads to separation into many soluble proteins and an insoluble protein residue. The effect of molecular size and shape on protein cohesive strength was demonstrated by measurements of tensile strength and elongation of films cast from laboratory preparations of wheat gluten, gliadin, and glutenin (Wall et a1 1969). Glutenin consisting of larger, more asymmetric 25 molecules forms films with greater tensile strength than gliadin films. Gliadin films stretch further than those from glutenin because of weaker molecular associations. Gluten, a mixture of gliadin and glutenin, has intermediate film properties. Reduction of the disulfides of gliadin increases its viscosity significantly due to unfolding of the polypeptide molecule. Reduction of glutenin destroys its cohesive nature when hydrated, but the reduced proteins are very sticky and quite adhesive. Because of the existing gluten proteins, hydrated flour can be worked into an elastic-cohesive mass by mixing. During mixing, the asymmetric glutenin molecules orient and associate, thus increasing dough strength. Orth et al (1972) investigated the relationship between flours, the variation in dough strength, and their different protein fractions. They discovered that the mixing time requirement of dough and the tolerance to mixing correlates to the residue protein content. Stronger flours not only contain more residue protein but also more of the higher molecular weight glutenin fraction. Glutenin molecules, (large asymmetric shape) have considerable surface area with numerous exposed functional groups to permit strong association by noncovalent forces. Fragments of highly crosslinked residue proteins contribute lateral cohesion and resistance to laminar flow (Hoseney et a1 1969). Gluten's cohesive-elastic character holds 26 ingredients and provides a chewy texture which is the basis for many vegetarian-simulated meat products. Most globular or albumin plant proteins exhibit little cohesive or adhesive properties in their native state. At a pH of 9 or above, however, disulfide bonds cleave, protein unfolding occurs, and functional groups previously associated within the molecule become available for external binding. Adhesion and cohesion are properties of many polymeric substances including proteins. Protein's high molecular weight and random coil structure result in more associations and the refore enhance adhesive and cohesive properties. The functional properties of proteins in foods are determined by the molecular composition and structure of the individual proteins and their interactions with one another and with other substances (Wall, 1979). Altering the constituent proteins or adding other proteins could improve or modify food characteristics such as viscosity, texture, water absorption, or fat emulsification. Proteins of wheat flour govern the plastic and elastic properties of bread doughs and some types of batters to a large extent (Pomerane, 1964). The relationship is most prominent in bread doughs, but the influence of flour proteins on the physical properties of the doughs and of batters is much less prominent and less understood. Protein consists of alpha-amino acids linked by peptide bonds 27 between the carboxyl group of one amino acid and the alpha- amino group of a second amino acid. This peptide backbone structure constitutes the primary structure of proteins. Dough derives its properties from the constituent components (Pomerane, 1964). The major and most important group of constituents is the proteins. The wedge and adhering proteins in the intact grain, or the derived fractions such as gluten, globulins, albumins, and lipoproteins are included in this group. The carbohydrates are the most abundant group, including starches, sugars, and soluble and insoluble polysaccharides. The lipids form a small but significant part of the flour. Water plays a key role in dough formation. Air forms the nuclei of the gas cells, and the oxygen acts as an improver. The amount of protein determines the density while the quality of protein determines the behavior of the three dimensional gluten network which permeates the dough (Swanson, 1943). Using higher protein flours, with the same quality but higher protein content, will result in larger loaf volumes. If flour has a high percentage of protein, the gluten mesh-work will be denser. Osborne (1907) separated the wheat protein into four distinct proteins: leucosin, water soluble; globulin, salt soluble; gliadin, alcohol soluble; and glutenin, insoluble. Based on a protein's structure, composition, solubilities, and other characteristics, it is classified as a simple 28 protein, conjugated protein, or derived protein. The most prominent component, gluten, is composed of two proteins, gliadin and glutenin. These two proteins effect baking quality. Upson et al (1916) studied the swelling of wheat gluten. Wheat proteins swell in water and especially in solutions of dilute acids because of the entrance of water between the protein molecules and the molecular structure. During the swelling process, gluten becomes softer, more flexible, and due to diminished cohesion, increases in weight and volume. Phosphate protein interactions could be responsible for lowering hydrogen bonding activity and subsequent reduction in water binding, extensibility, and cohesion (DeMan et a1, 1976). The increase in free water may be among the factors explaining lower resistance to extension of overmixed dough as well as its wet and sticky appearance. The viscoelastic properties of wheat dough are primarily attributed to gluten proteins. These proteins form a network of linear macromolecules bound together by various cross-links during the process of dough development. Because of the high concentration of glutamine in gluten- forming proteins (about 30%), a great number of hydrogen bonds form, rendering this protein fraction insoluble. Using microscopic examination, three phases, starch, protein, and gas cells, can be distinguished in an unleavened dough, and yeast cells constitute a fourth phase 29 in a leavened dough (DeMan et a1, 1976). All starch kernels retain their identity in dough and are embedded in a continuous matrix of protein. A fine, vesicular structure with expanding gas cells is developed and maintained during fermentation and proofing until heat fixes the texture in bread by protein denaturation and starch gelatinization in the oven. The tendency of dough, and particularly gluten, is to spread into films having great stability and with time- dependent surface viscoelastic properties, while still being highly compressible. Glutenin forms a very tough, rubbery mass when fully hydrated, while gliadin produces a viscous, fluid mass upon hydration (Pyler et a1, 1973). Glutenin is a prime contributor to the functional properties of gluten and dough (Bietz et al, 1973). Wheat dough's characteristics of viscoelasticity and loaf volume are primarily due to the gluten protein consisting of glutenin, gliadin, and small amounts of albumins and globulins. Hydrated glutenin is tough and cohesive, but less elastic than the whole gluten, while hydrated gliadin yields only a viscous mass. Accordingly, the unique structure and composition of gluten produces the rubberlike properties of dough. Glutenin constitutes approximately 30 to 40 per cent of the protein in wheat flour, and about half that in gluten. Because of cystine residues, disulfide linkages can 30 occur either within (intra-) or between (inter-) protein chains (Bietz et al, 1973). These linkages determine the functional properties of native molecules. On the other hand, if all disulfides were of the inter-chain variety, the resulting highly branched polymer would not allow suitable alignment of proteins to form a dough. To form a dough an optimum balance of inter- and intra- chain disulfide bonds is essential for good glutenin performance. Glutenin occurs only in the endosperm, and probably serves both as structural protein and as reserve material for the seed. Too much glutenin may prevent expansion of gas cells during fermentation (Mecham, 1973). An appropriate combination of glutenin and gliadin is essential for good dough performance and loaf volume. Glutenin molecules, because of their high molecular weight, shape, and their amino acid composition, impart toughness and strength to gluten. These molecules are favorable for hydrogen and hydrophobic bonding and provide relatively large surface areas which are suitable for molecular association. However, if glutenin is the only protein fraction in dough, the dough would be too resistant to expand during fermentation and baking. To assure good performance of the dough, gliadin, with its small and symmetrical molecules must be present to modify the glutenin. Gliadins are mixtures of tightly folded globular 31 proteins with hydrophobic regions buried within the molecules and the hydrophilic H bonding regions exposed on the surfaces (Mecham, 1973). This structure may explain the sticky nature of gliadins. The factors that contribute to the strength of an adhesive joint (Gent, 1982) range from weak Van der Waals interactions to covalent chemical bonding, which plays an important role in the attractive forces at the interface. Besides these, the dissipative properties of the adhering materials are also contributing factors. On the other hand, perfectly-elastic and non-dissipative materials have the lowest adhesion strength. There are also geometrical factors in joint strength. When the adhesive layer is extremely thin, it cannot release much energy in the internal deformation processes, which keeps its contribution to the observed strength to a minimum. The energy required for joint rupture is stored elastically in the bonded parts (Gent, 1982). When energy is expended, this makes a small detached region grow in size. The result of this action shows that the breaking stress depends upon the elastic properties of the system (the elastic modules and dimensions of the various components), and the size of the debonded zone. At least three sciences contribute to the strength of adhesion: interfacial chemistry, rheology of inelastic materials, and the mechanics of fracture of composite systems. The first 32 phase of dough formation primarily involves the moistening of the flour particles. The movement of the mixer elements an/or bowl disperses the dough water between the flour particles. The hydrophilic properties of the particles cause liquid to be absorbed onto their surface. This results in the shearing elements of the mixer countering the forces of adhesion. 2.2.3 Measurement of physical/functional properties of dough The most distinctive property of dough made from wheat flour is its ability to retain the gas formed within its mass either due to the growth of yeast or the action of an acid on sodium carbonate (Swanson, 1943). This property results from the water films absorbed on the filaments of gluten and the enmeshed starch. There is a certain amount of elasticity and plasticity in gluten strands, enabling recoil after stretching and if the stretching goes beyond the elastic limit, it results in permanent elongation. The Brabender farinograph is used to measure the water absorption properties of flour and the mixing characteristics of a standard flour-water dough. Because of the complex nature of the functional properties of wheat flour, an evaluation of wheat flour dough must be performed under actual or simulated baking conditions. The brabender farinograph and extensigraph are the basic instruments used to characterize the gluten proteins under the simulated conditions existing within the bakeshop. 33 Dough consistency plays an important role in achieving proper mechanical development. It also influences the gas retention properties of the dough (Sietz, 1978). Absorption values are used extensively in the calculations involved in developing new formulations. Generally, flour with high absorption values are desired because it increases unit yields. 2.3. Correlation of measurement in stickiness with food The force to tear products apart per cross-sectional area or per unit weight of sample is a function of a material's tensile strength. Tensile strength was used to measure the adhesion strength of chunked and molded products (Trout and Schmidt, 1987). Tensile strength is often measured using an Instron Universal Testing Machine, or a device such as the Food Technology Corporation's Texture recorder, which measures an apparent tensile strength. The Instron Testing machine was introduced in 1949 (Hindman & Burr) as a general purpose material testing machine, and is used for testing textiles, paper, plastics, rubber, and other flexible materials. It is suitable for laboratory use because of the sophisticated controls and sensitivity of measurement possible. Its most useful function is in the application of classical material test methods to establish fundamental material properties. The Instron Tensile Tester, model TM (Instron Engineering Corp., Quincy, M.A.) consists of two horizontal, 34 parallel plates, with a constant rate-of-jaw-separation on the tap plate. A device attached to the bottom plate measures the force pressing (positive) or pulling (negative) against the plate (ASTM D 882-83, 1983). The crosshead is set and moves at a constant rate during the test. The stickiness value equals the grams adhesive force and cm crosshead movement times the appropriate factor. The Instron Tester is an excellent tool to evaluate stickiness because it focuses on the surface properties most desirable to measure. Batcher et al (1963) stated that cooked rice had similar palatability characteristics no matter what cooking method or medium was chosen. Ferrel et a1 (1960) used a screening device constructed so as to determine if different preparation methologies would change the rice stickiness. Mossman et a1 (1975) studied different treatments that accelerated the aging of sticky rice. In each case the Instron Tester was chosen to measure stickiness levels and to differentiate the type of stickiness. Mossman et a1 concluded that time and water content had varying impact on the stickiness of the sample. Increasing cooling time resulted in a small increase in the stickiness value, while an increase in the amount of cooking water caused a proportionately greater increase in the stickiness value. 35 2.3.1 Methods of measurement in stickiness Cooked spaghetti must be firm, resilient, and nonsticky to meet maximum consumer acceptance. Voisey et a1 (1978) used the Instron Universal Tester to measure the stickness of cooked spaghetti. D'Egidio et al (1982) concluded that spaghetti stickiness is related to the amount of surface material that can be washed from drained cooked spaghetti. Compression testing utilizes a compression cell which is composed of parallel plates between which test procducts can be compressed. Apparent stress at failure and apparent strain at failure can be calculated (Diehl et al., 1979), while true stress and strain cannot be calculated because a uniform cylinder is not maintained during compression. Strain is highly correlated to sensory and texture profile analysis (TPA) cohesiveness, while stress to fail (compressive force to failure) is correlated to TPA hardness and sensory firmness (Montejano et L., 1983). Dexter et a1 (1980) modified the GRL compression tester (Kilborn et a1, 1982) to test for cooked spaghetti stickiness. Dexter's process used sample sizes as small as 6g of spaghetti. The cooked spaghetti was compressed under a plunger and the force of adhesion of the spaghetti to the plunger was measured upon lifting the plunger. Dexter demonstrated that the quality of the cooking water and spaghetti drying procedure have a significant influence on stickiness of cooked spaghetti. Spaghetti 36 stickiness is also related to cooking time and elapsed time after cooking. Other factors such as gluten strength, sprout damage, semolina granulation, and extrusion conditions are all associated with cooked spaghetti stickiness. Dexter concluded that protein content has no significant correlation to spaghetti stickiness. Dexter et a1 (1983) studied factors that influence stickiness and their relationship to other cooking quality characteristics. He concluded that each spaghetti sample proved to be stickier and lost more solids during cooking when cooked in tap water compared to deionized water. Comparing spaghetti processed under high temperature and low temperature drying conditions, spaghetti cooked at high temperature was less sticky. Stickiness was lightly influenced by cultivar, wheat class, raw material granulation, and protein content, but was not related to sprout damage. Even when all the factors were included in a step-up regression analysis, less than 50% of the variance in stickiness could be predicted. Gaines et al (1982) studied the influence of temperature, humidity, and flour moisture content on stickiness in sugar-snap cookie dough. Dough stickiness measurements were conducted with a Struct-O-Graph. Gaines concluded that the most desirable ambient conditions for evaluating soft wheat cultivas with the micro-method III (Finney et al 1950) procedure are 37 temperatures between 20-21°C and 30-50% relative humidity. This allows "standardization" of dough consistency and also prevents stickiness problems. No combination of flour moisture content and dough water absorption level caused stickiness problems at 21°C and 50% relative humidity. At optimum dough consistency, doughs made from flours having high moisture contents were less sticky and easier to work with because they tolerated changes in the level of dough water absorption better. Gaines (1981) used a Struct-O-Graph (C. W. Brabender, South Hackensack, N.J.) to measure the stickiness of cake crumb and to find out if flour chlorination correlated with cake crumb stickiness. A Struct-O-Graph was fitted with a 2,000-cmg spring and a 30-mm diameter plastic disk plunger that moved at a rate of 132 mm/min. The pen arm was activated at the 500-BU chart line, when the cake crumb piece had been compressed for 1 minute, and stopped at the 1,000-BU chart line. At this point compression was relieved and the stickiness measurement was taken. This can be described as one compression/stickiness measurement cycle. When compressing the sample, the pen arm will travel above the 500-BU line if the sample adheres to the disk and platen. The distance above the 500 line is recorded as the amount of crumb stickiness in centimeter grams. The mean of the stickiness measurements is then calculated. Higher mean stickiness values indicate greater crumb stickiness. 38 Neither flour chlorination rate nor the flour pH, cake volume, or batter liquid level were correlated with an objective stickiness measurement. Taguchi et al (1979) studied the factors affecting the adhesion of canned mackerel meat. Measurement of adhesion consisted of weighing the meats that adhered to the inner container. Taguchi used the following for his study: Different retorting time: 80 minutes and 60 minutes Salt: 2.5% NaCl, 2.5% NaCl + 0.2% pyrophosphate, or 2.5% NaCl + 0.1% CaClz; Heating times, 40° to 100°C for 30 minutes. He concluded that the freshness of the raw meat influences the degree of adhesion while the heating temperature affects the formation of adhesion bonds. The most noticeable adhesion occurred when the internal temperature reached 60°C. Adhesion increased greatly as the heating temperature reached 80°C without NaCl or with 2.5% NaCl. The amount of adhesion greatly decreased with the addition of CaCl2. Curley et al (1983) studied the effect of corn sweeteners on dough stickiness. Dough stickiness was measured with the Instron Universal Testing Machine (model 1122) in the tension mode. He concluded that the dough with 0% dissolved sucrose was firm and manageable, while the one with 100% dissolved sucrose was very sticky and unmanageable. When 50% of the granular sucrose was replaced 39 with High-fructose corn syrup, the resultant dough was as sticky and unmanageable as the dough made with 100% dissolved sucrose. Noguchi et al (1976) studied the correlation of dough stickiness with various quality parameters. A texturometer (General Food Corp. New York) was used to determine dough stickiness and consistency. Dough was mixed with a 1.5% sodium chloride solution in a pin-type mixer and the dough was shaped into a sheet (15 x 5 x 1 cm) by the Chopin alveograph mixer and then set on the texturometer. Noguchi concluded that dough stickiness correlated very highly with the sulfhydryl (SH) content of the protein and with proteinase activity. The protein content, however, did not correlate with adhesiveness, but possibly those with a high sulfhydryl content might well be expected get involved. In the butter industry, the term stickiness refers to the property which permits butter to remain attached to solid surfaces. This physical characteristic, which involves both adhesion and cohesion, has been described by the term 'hesion' (Claassens, 1958). Thomasos et al (1963) studied some factors which influence butter stickiness. He pointed out that the characteristic crystal structure affected the hesion values, and homogenization of butters significantly increased hesion readings. An increase in gas content caused a decrease in hesion values with more butter remaining on the adherend. 40 Thomasos also stated that the crystal structure would change the adhesive property of butter and the gas content would influence the cohesive property. Kumar et al (1975) compared a balance and a sieve to test the stickiness of cooked rice. Juliano et al (1965) concluded that stickiness related to the amylose content of rice. Sanjiva (1938) stated that rice stickiness is strongly affected by its age, that freshly harvested cooked rice is moist and sticky, but that aged cooked rice is dry and flaky. 20 g of cooked rice was placed on the top sieve (6.7 mm). The two sieves were rotated by hand, with a firm tap at the end of each rotation. After sieving, the rice retained on each sieve was carefully collected and weighed. To conduct the adhesion test, 10 g of cooked rice was placed in a stainless steel cup, gently levelled with a spatula and then pressed for 4 minutes with a 1.5 kg metal pressure weight, and passed through a vertical guide to give a uniform surface. A polished stainless steel cylindrical test body hanging from the left arm of a balance, and counter-balanced exactly on the right arm, was then gently lowered onto the rice and pressed with another small pressure weight for exactly one minute. The weight was removed, the balance released, and sand was added in a stream onto the right pan until the test body was released from the rice. 41 Kumar came to the conclusion that the sieve test gave a very good indication of the stickiness of cooked rice. The adhesion test, although providing indication of the stickiness of cooked rice had a low correlation and the test procedures needed further improvement. He concluded that the consistency of Cooked rice has a negative correlation with stickiness but the water insoluble amylose content of rice seemed to have significant correlation. CHAPTER 3 MATERIALS AND METHODS This research is divided into two parts. In part 1, studies were designed to evaluate the stickiforce meter as a device to measure adhesion between dough and the contacting surface. In part 2, studies were designed to characterize adhesion between plastic films and doughes of different flour types and protein levels. 3.1 Materials 3.1.1 Flour Samples A dry mix (flour plus premix), provided by a Pizza Manufacturing Company, was used for the phase I study. In the phase II study, three different flours were selected. Bleached, enriched bromated flour and unbleached, unenriched pastry flour were purchased from Food stores at MSU. The flours were manufactured by General Mills, Inc., Minneapolis, Minnesota. Premium, high gluten, bleached, bromated flour was purchased from Food Stores at MSU and was manufactured by Bay State Milling Co., Quincy, Mass. 3.1.2 Film Samples Film samples were obtained from several suppliers and the pizza manufacturing company for phase I study. (Table 1) In the phase II study, three different films were selected 42 43 Table 1. Film samples used in Wettability and Stickiforce Meter - Phase I study Material Film thickness 1 HDPE 20 MIL (High Density Polyethylene) 2 PVC 15 MIL (Polyvinyl Chloride) 3 PET/RELEASE AGENT 14 MIL (Polyester) 4 PETG 8 MIL (Polyethylene Terephthalate Glycol) 5 2% EVA/VEGETABLE OIL 2.5 MIL (Ethylene Vinyl Acetate) 6 2% EVA/1.5% PAM SPRAY 2.5 MIL (Ethylene Vinyl Acetate) 7 2% EVA/MYV 9-40 2.8 MIL (Ethylene Vinyl Acetate) 8 TRI-EXTRUDED PE 0.7 MIL 9 KRAYTON 14.5 MIL 10 60 1b. SEMI-BLEACHED 4.0 MIL SILICONE COATED RELEASE LINER 11 TEFLON FEP 1.0 MIL 12 SILICONE RELEASED PAPER 3.5 MIL 13 SILICONE ON SUPER * CALENDARED DENSIFIED KRAFT 14 SILICONE ON CLAY- * CALENDARED DENSIFIED KRAFT Sources DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza DOMINO'S Pizza MEAD RELEASE PRODUCTS DU PONT/DURAFILM MEAD RELEASE PRODUCTS EASTERN FINE PAPER EASTERN FINE PAPER * Silicone coated materials - thickness unknown 44 to provide a broad range of surface wettability and morphology (Table 2). Both PET and Teflon films were obtained from E. I. Du Pont De Nomours & Co., Inc. (Circleville, Ohio). LDPE film was obtained from Tredegar Film Products (Manchester, Iowa). 3.2 Analytical Measurements 3.2.1 Determination of the Initial Flour Moisture Content (IMC) Moisture analysis were performed on the Hi-protein flour, bread flour, and pastry flour. Triplicate 2.0 (~2.000) gram samples were weighed on an analytical balance, then dried to a constant weight in a Hotpack Vacuum Oven, Model 633 (Hotpack Corp., Philadelphia, PA.) at 80°C in a partial vacuum of 30 mm of Hg for 6 hours, according to AACC Method 44-40 (1983). The dried samples were transferred to a desiccator until cooled to 25°C and then weighed to the closest 0.0001 gram using a Mettler AE 166 Balance (Mettler Instruments Corp., Hightstown, N.Y.). The samples were reweighed to determine weight loss due to loss of moisture. IMC was determined (dry basis) according to the equation: (W1 - Wf) / Wf * 100% = % Dry Wt Where W1: Initial weight of product sample . Wf: Final weight of product sample after drying 45 Table 2. Film samples used in Wettability and Stickiforce Meter - Phase II study Film Thickness Low Density Polyethylene (LDPE) 2 MIL Polyester (PET) 1 MIL Teflon 2 MIL 3.2.2 Determination of the Protein Content Protein content of the pastry, bread, and high gluten flours were performed using the Microkjeldahl method (according to AACC method 46-13) for total nitrogen determination. Duplicate 0.5 gram samples were digested in sulfuric acid, sodium sulfate, and copper sulfate at 400 - 500°C until digestion was completed (#2 hours). Samples were transferred to a distillation apparatus (Buchii Kjeldahl Machine, Brinkman Instruments) and distilled according to AOAC Methods 2.057, 14.026 and 14.068 (1980). Total protein was calculated based on percent nitrogen in the sample multiplied by a factor of 5.7. 3.2.3 Determination of the later Absorption Properties -Parinogaph Flours were evaluated for water absorption using a Farinograph, manufactured by C.W. Brabender Instruments, Inc. (Model PL-ZH, Dynameter number 2092). A Thermobath 46 (Type P 60-B) maintained at 30+/- 0.1°C was used to regulate temperature of the mixing bowl. The test was run according to AACC Method 54-21 A (1983). Moisture content of the pastry, bread, and Hi- protein flours were determined as described previously. 3.2.4 Stickiforce Meter Determination Lai et a1. (1985) applied a modified tensile strength apparatus to measure powder cohesiveness. Similar principle was used by Lai in developing the Stickiforce Meter. The base, dough holder cube, and cube stopper were constructed from plastic (Acrylic)(Fig. 2). The cube was open at both ends. During measurement, a small piece (2" x 2.5“) of test film surface is placed under the cube opening. The cube is then filled with dough sample (~27.5 g) and placed sideways against the stopper of the apparatus. The test film material is attached to a string with a small cup at the other end. The test film surface is made to break away from the dough surface by the weight of water added into the cup from a burette (50ml). The weight-force per unit area of separation (Wtforce) is recorded. In addition, the weight of the contact surface before and after each test was also measured. This was reported as weight-mass per unit area (thass). 3.2.5 Inclined Plane Determination The wettability of a surface can be determined by the sliding of a drop of fluid along a tilted surface (Kawasaki, 47 2 // /;4/ M 7 / Figure 2. Diagram of Stickiforce Meter. Components: 1. Base (Acrylic) 2. Dough holder cube 3. Test film 4. Burette 5. Burette holder 6. Cup 7. Cube stopper 48 1960; Bikerman, 1966). The tilted plane procedure described by Lai (1988) was adapted for use in this study (Fig. 3). It provided a measure of the wettability of the plastic surface. A droplet of distilled water and 50% ethyl alcohol were placed separately on the test surface which lay on a horizontal platform. The droplet was allowed to spread until arrest occurred. The platform was then carefully tilted at a rate of one degree per second. Angle of slide was defined as the limiting angle between the platform and the horizontal plane at which the droplet moved at a uniform rate of one degree per second. 3.3 Experimental Design 3.3.1 Phase I Study Studies were designed to evaluate the stickiforce meter as a device to measure adhesion between dough and the contacting surface. The Stickiforce meter was then used to determine if different dough temperature and contacting films would effect sticking of dough to film. Films (Table 2) were cut into 1" x 8" strips using a JDC Precision Sample Cutter Model JDC 25 (Thwing - Albert Instrument Company, Philadelphia). Fresh dough was prepared by weighing out 0.91 grams of active dry yeast, and 481 grams of 35°C tap water. A small portion of the water was slurried with the dry yeast in a mixing bowl. One package of the prepared dry mix (flour 49 Plastic Film J °‘~ - angle of the tilt Figure 3. Sliding of a drop of fluid along tilted plane. 50 plus premix) was then added to the bowl, along with the remaining water. These materials were then mixed in a Kitchen Aid K-Sss Mixer (Hobart Corporation, Troy Ohio, speed range 2) at room temperature for seven minutes or until the dough was fully developed. After development, the surface was dry and shiny and the texture very fine. When the dough was stretched by hand, there was a good deal of elasticity and stretchiness. Treatment Variables A. Fresh prepared dough was placed in contact with film surface. Following refrigeration (4°C) for 24 hours, each sample was allowed to reach ambient temperature (23°C) and proofed to twice its original size (approximately 4 hours) before performing the Stickiforce Meter Measurement. B. Same as treatment A except that the dough was put inside a plastic bag (LDPE) under refrigeration for 24 hours. The dough was then placed into contact with the film surface, and proofed to double its size before performing the Stickiforce Meter Measurement. C. Same as treatment A except that dough was not refrigerated. Stickiforce Meter Measurement was performed after the dough was proofed to twice its size (approximately 2.5 hours) at ambient temperature (23°C). D. Fresh dough was proofed first at room temperature (23°C) and then placed in contact with the film surface for Stickiforce Meter Measurement. 51 These four treatment combinations were arranged in a 2 x 2 factorial design. The effect of yeast condition (proofing), and temperature were evaluated, as well as the interaction of these factors. A split plot design was used. Treatment variables served as the whole plot factor and film as the split of a randomized complete block design. 3.3.2 Phase II Study Studies were designed to characterize adhesion between plastic films and doughes of different flour types and protein levels (Fig. 4). Several plastic packaging materials were selected from Part 1 to provide a broad range of surface wettability. Flour of different protein and starch contents were obtained and blended with water to form model systems. These were deposited onto the surface of selected packaging materials. The influence of protein concentration on adhesion was also determined. In addition, the flour protein was fractionated and studies of adhesion conducted with individual proteins. Dough was also prepared at several protein concentrations and adhesion characterized for fresh dough, refrigerated, and proofed dough systems. Dough Preparation Three-hundred grams of flour were mixed in a Kitchen Aid K-SSS mixer (Hobart Corporation, Troy Ohio) at room temperature. Red Star quick-rise active dry yeast (1%) was r—gi 56:35:39.. .2591 . loan—Nb \ Pm.— \ mm 133m >~=h, x w '3 w § § 0.002 {if . \ l 8 \i i i \ \ ) ) o) 8 \\\ §\ (\ i k .4 4) FIgtn11.Th0W0mvduu0fpr0dMandma-flmmdouoh atroantanpomnnm'C). 0.2 A - Moot-mu M: g < Contact-(Int hut s 0.15 - E g 0.1 - i 0.05 - OJ 8) 9. 4.4.4; .4 4 3* .~ .4 . '9 \ ‘ \ I ° 0 . 4" 6“) 4‘" ‘9? 4» 400:3”!67’. «'9 Q FIgura12. mwumvuuesdpmdmwmammdqm atmfllgomedtommumuw). 71 Honestly Significant Difference test results of thass values are listed in Appendix B, Table 19. Proof-first and contact-first yeast dough had the same amount of yeast and the same fermentation time, but appear to yield totally different results. The reason could be that after contact-first-yeast dough reached full maturity, the web structure reveals thin-walled gluten strands that were dry and mellow and offered minimum resistance to stretching when pulled. Proof-first-yeast dough reached a fully fermented stage, and was then put in contact with the films and the test (Stickiforce Meter) was performed immediately. Thus, there wasn't any opportunity to bring about a relaxation of the stresses created within the dough by the mixer action. Apparently, the lack of a second fermentation period resulted in these stresses not being released. This may be the reason why proof-first-yeast dough proved stickier than contact-first-yeast dough. Wtforcg The type of film has significant effect on dough stickiness. Significant differences were found among all films for Wtforce (F = 69.605, p = 0.0000). Tukey's Honestly Significant Difference test result of Wtforce (Appendix B, Table 20) indicated that there was no significant difference among HDPE, PVC, PET, and PETG; no significant difference among PETG, 2% EVA/OIL, 2% EVA/PAM, 2% EVA/MYV, Tri-extruded PE, Krayton, and ISO-60; and there 72 was no significant difference among 2% EVA/MYV, Tri-extruded PE, Krayton, ISC-60, Teflon FEP, Silicone released paper, 80C146A, and 78698. The interaction between film type and yeast condition was highly significant (F = 168.226, p = 0.000) for Wtforce (Fig. 13). The effect of film type or yeast conditions on the Wtforce value is dependant on each other. As figure 13 shows, Wtforce values of proof-first-yeast dough were higher than those of contact-first-yeast dough. Wtforce values for 78G98/Proof, PETG/Proof, ISC-60/Proof, and Silicone released paper/Proof were higher than the rest. Apparently, the silicone release agent didn't function properly. Tukey's Honestly Significant Difference Test Result of Wtforce values (Appendix B, Table 21, Fig. 14) indicated that there was no significant difference among 78G98/Proof, PETG/Proof, Silicone/Proof, ISC-60/Proof, Silicone/Contact, and 80C146A/Proof, no significant difference among PETG/Proof, 80C146A/Proof, PET/Proof, PVC/Proof, 80C146A/Contact, 78G98/Contact, ISC-60/Contact, and HOPE/Proof. Also there was no significant difference among EVA/OIL/Proof, Krayton/Proof, PET/Contact, EVA/OIL/Contact, HDPE/Contact, PETG/Contact, PVC/Contact, EVA/PAM/Proof, Krayton/Contact, EVA/MYV/Proof, Teflon/Proof, Tri/PE/Contact, EVA/MYV/Contact, and Teflon/Contact. The materials (Table 1) can be categorized into four groups. The EVA films with different coating materials w'r-roncn (salon-89) M 00 N O J .5 G l .5 O l 0 73 - Proof-mu mm \\ . 81§§18§i3 4 54,4 _, r? 4’ “° ”8.45454 L_ ///////x Contact-(mt hut /////////////¢/i’/f/ k \ ) \)\ 4" f?" f ‘94 Q FIou'e13. TheWIIomavduudproaI-Ihummammdough 0 Contact-first onvarIousIIm “' HDPE WT-FORCE (GM/CM-SO) + PVC * PET "' PETG * EVA/OIL *' EVAIPAM * EVA/MYV + TRI/PE ‘.' KRAYTON ‘* ISC-BO * TEFLON ‘" SILICONE *BOCMGA Proof-fits! t- 78698 .Floue14.Tut0y'sHSDteaW00roomvduadvmtypesdmatw mmmwmmm 74 (coated with vegetable oil, 1.5% pam spray, and myv 9-40), Teflon, Krayton, and tri-extruded PE high slip film as good release materials, PET with release agent as medium release material, silicone release agent coated materials (silicone released liner, silicone on super-calendared densified kraft, and silicone on clay-calendared densified kraft), and HDPE, PVC, and PETG as poor release materials. MYV 9-40 is a grouping of food emulsifiers, dough strengtheners, and softeners, coatings. It consists of texturing/aerating agents, and lubricants, made of edible lard. Liquid MYV 9-40 materials are used to stabilize the viscosity of chocolate-flavored syrups. MYV 9-40 can provide a bland, edible, protective coating on food products to improve their shelf life, texture, appearance, and stability. They are waxy rather than greasy, and have extremely good oxidative stability and good oxygen and moisture barrier properties. When a 0.25 percent level of MYV 9-40 was sprayed on dates and raisins, it reduced their stickiness for easier handling in automatic equipment. Also these agents can be sprayed on food as surface lubricants and on processing equipment for use as a lubricant or release agent (Eastman Chemicals, 1986). Silicone is widely used as a release coating on plastic film label stock. Small amounts of specific silicones are used as internal and external mold release agents, process aids, and flame retardants in thermoplastics (Bafford, 75 1987). In our study, the materials coated with silicone release agents were quite sticky compared with other groups of materials, and the reason is unknown. PVC, PET, and PETG all have very polar surfaces. According to Young (1805), surface tensions exist at the phase boundaries of a drop of liquid at rest on a solid surface (Fig. 1). If the molecules that make up the surface are more polar, the surface is easier to wet and bond with a polar liquid adhesive. PET film was treated with release agent to decrease its stickiness. HDPE film is not as polar as PVC and PETG. Temperature has significant effect on dough stickiness. Significant differences were found between refrigerated dough and room temperature dough for Wtforce (F = 312.657, p = 0.000). After the dough was mixed at room temperature (23°C), it was then put in the refrigerator (4°C) for 24 hours. As a result, when the dough was taken out of the refrigerator it may have been drier than when it was put into the refrigerator. When the dough was removed from the refrigerator and left at room temperature, sweat appeared on the surface of the cold dough, causing condensation to occur. This condensation may have been the reason why the dough was more sticky. The effect of film type varied between the two temperature conditions. The Wtforce values at refrigerated temperature were higher than those at room temperature (Fig. 76 15). Figure 14 shows that 60 lb. semi-bleached densified kraft film (ISC-60) at refrigerated temperature had the highest value among all tested. Tukey's Honestly Significant Difference test results of Wtforce values (Appendix B, Table 22, Fig. 16) indicated that temperature had different effects on the different films. The effect of yeast condition on Wtforce (F = 7.905, p = 0.000) also depended on temperature (Fig. 17). The mean values of Wtforce at refrigerated temperature (4°C) were higher than those at room temperature (23°C). The means of Wtforce values for proof-first-yeast dough were higher than those of contact-first-yeast dough. Tukey's Honestly Significant Difference test results of Wtforce (Appendix B, Table 23, Fig. 18) indicated that proof-first-yeast dough at refrigerated temperature differed significantly from others. A three-way interaction of film, yeast, and temperature was highly significant (F = 8.843, p =0.000) for Wtforce. This three-way interaction is illustrated in Figure 19 and 20. Dough stickiness varied when either yeast condition, temperature, or film type changed. As discussed above, different films have different wetting characteristics. Stickiness varied with yeast condition and the change in temperature. In general, stickiness values were higher with proof- first-yeast dough than with contact/first-yeast dough. Stickiness values were higher when dough was stored at 77 26 - Icon M04231?) mm. To”. (re) c? 20 - *5) 5 6 16 ~ N viii g ‘° ‘ 35$. \\ \ )1“; ‘3 i s- \‘ \ 1) 1 ) 4. o .9 M015. mmwmdmwmw dough on val-lam Ilm 35 * HDPE + PVC m . * PET ‘ + PETG 8, 25 * EVA/OIL 5 '0' EVA/PAM \ 20 5' , + EVA/MYV u.) q i "" TRI/PE g 15 ~ ' e * KRAYTON * TEFLON . * SILICONE - — ~ -- . ' + 800146A - Floure16. Tukey'sHSDtestWUOrcomnvaIueadvumtyposdmeml atroomandromoomodtompomm. 79 10 “_ - Moot-flu! You! § comm-11m 11...: g 12~ .. \' ' v < 5 5 E \5 \\ \ \ \\ \\\\\§5 ‘5\§\\\:\5 555555555y555 @7493 " 4* P g _ {5.53.5 ‘5”! 04“ng FIoInIO. mmmdmmummmam atrocman'C). so - "account we - comm-11m mu § 26 ~ I g 20 ° 8‘ \ 8 5i: '2 5 :1‘ \\ \5 53 \ ii“: ‘ )5: \\ k \\ \‘55 55 N is: ”4944,4435! $44!; mum. TMWfloroovduudptooI-IIMIMWMMM "WWWQ- 80 refrigerated temperatures than when dough was stored at room temperatures. However, there were a few exceptions. For PVC, the Wtforce value for contact-first-yeast dough was higher than those for proof-first-yeast dough. The Wtforce values at refrigerated temperature (4°C) with proof-first- yeast dough were higher than those at room temperature (23°C) with contact-first-yeast dough. Proof-first-yeast dough on 78698 at refrigerated temperatures had the highest Wtforce values and contact-first-yeast dough on Teflon at refrigerated temperature had the lowest Wtforce values among all tested. Comparing the Wtforce mean values with different factors, silicone coated materials had the highest Wtforce mean values. Tukey's Honestly Significant Difference test results of Wtforce values are listed in Appendix B, Table 24. 4.2. Phase II study 4.2.1. Inclined Plane Determination In this study, the wettability of the film surface was also determined using a modified, inclined plane apparatus. Table 9 presents the results obtained for the different film systems. The resultant angle of slide for the surfaces studied ranged from 25.1 to 33.8 degrees. Teflon film had the smallest angle of slide (25.1°). This indicates poor wetting of the material. The PET surface had the largest angle of slide (33.8°). 81 Table 9. Wettability of distilled water and 50% ethyl alcohol on different material surfaces. Distilled water 50% ethyl alcohol WW W Machine Cross Machine Cross Direct, nirggty Direct, Direct. LDPE 29.911.92 29.8:2.04 24.912.26 26.3:2.93 PET 33.8il.94 32.9:2.26 32.3:2.14 32.013.07 TEFLON 25.112.46 25.7i1.40 22.3i0.87 23.911.28 4.2.2 % Protein in Flours Doughes of different protein concentrations were prepared by mixing water with flours of different protein contents. The amount of protein in the three different flours is shown in Table 10. Based on the results of the Farinograph measurements, water (Appendix A) was mixed into the flour systems to optimize dough consistency. Dough mixing time was also optimized using the results of the Farinograph evaluation. Doughes from each of the different flour mixtures were then applied to the three test films (Teflon, PET, and LDPE) and tested for Wtforce and thass as previously described. 4.2.3. stickiforce Hater Determination The doughes were made of Hi-protein, bread, and pastry flour. Table 11 shows the effect of dough treatments on the 82 Table 10. The percentage protein in pastry, bread and Hi- protein flours - determined using Microkjeldahl method. W .LL_9_rot in Pastry Flour 8.76 Bread Flour 13.05 Hi-protein Flour 14.81 83 Table 11. The effect of treatment on the Weight-mass gain per unit (gm/cmz) determined by Stickiforce Meter W (Unit = 10'1) IBEAIHEHI L923 231 IEELQH E* 2.16:1.24 3.19:0.71 0.20:0.42 F* 2.1911.20 2.9610.73 0.29:0.27 0* 0.94:1.32 1.72:0.48 0.22:0.26 H* 2.2811.25 2.04:2.27 0.37:0.20 1* 6.38:1.52 3.95:1.13 2.09:0.63 J* 6.8311.13 4.2710.97 2.53:0.53 E*. Dough was put into a container, refrigerated (4°C), then was allowed to reach room temperature (23°C) and proofed to double its original size. Then it was placed in contact with the film surface prior to the test. F*. Dough (with yeast) was first proof to double its size at room temperature. Then it was placed in contact with the film surface prior for test. 6*. Dough (with yeast) was placed in contact with film surface. Refrigerated, then each sample was allowed to reach 23°C and proofed to double its size prior to the test. H*. Dough (with yeast) was placed in contact with film at room temperature. Test is performed after the dough was proofed to twice its original size. I'. Dough (no yeast) was placed in contact with film surface. refrigerated for 4 hours, then was allowed to reach room temperature before performing the test. J'. Dough (no yeast) was placed in contact with film surface. Test was performed after the dough was made. 84 weight-mass gained (per unit contact area) as determined by the stickiforce procedure. Treatment J (no-yeast dough contact with film surface, test was performed after the dough was made) had the highest weight-mass values for all contact surfaces. This suggests that dough made without yeast and held in contact under refrigerated temperature (4°C) had enhanced adhesion. The fully hydrated protein of a mixed and kneaded dough forms a veil-like film over the external surface of starch granules. The fractured surface of the inside of the dough exposes many cleaved starch granules embedded in a protein matrix with numerous microscopic holes (Christianson, 1975). After fermentation, this protein lattice structure shows larger air cells. Many of the small air cells enmesh minute starch granules within them. The veil-like protein coating on the surface of the starch granules, stretches and rolls up into fibrils due mainly to an increase in the size of the air cells. This may have caused the yeast doughes to be less sticky than the no-yeast doughes. Wtforce per unit area data obtained from the Stickiforce Meter is shown in Table 12. For both PET and Teflon film, treatment J had the highest Wtforce per unit area studied for all the contact surfaces. However, for PE film, treatment I (no-yeast dough contact with film, refrigerated, equilibrated to 23°C) had the highest Wtforce values. 85 Table 12. The effect of treatment on the Weight-force gain per unit (gm/cmz) determined by Stickiforce Meter .EILM_§AM£LE IBEAIMEEI RE 221 EFLON E* 34.93i8.54 35.12:8.08 20.73:7.37 F* 34.93:10.98 34.39:11.57 20.18:7.95 0* l4.69i7.67 17.7217.27 10.56:8.58 H* 20.8519.52 20.06:10.60 12.67i6.01 1* 53.24:9.31 49.86:7.33 37.3915.93 J* 50.18i6.47 50.0716.35 38.05i5.46 E*. Dough was put into a container, refrigerated (4°C), then was allowed to reach room temperature (23°C) and proofed to double its original size. Then it was placed in contact with the film surface prior to the test. F'. Dough (with yeast) was first proof to double its size at room temperature. Then it was placed in contact with the film surface prior for test. 6*. Dough (with yeast) was placed in contact with film surface. Refrigerated, then each sample was allowed to reach 23°C and proofed to double its size prior to the test. H*. Dough (with yeast) was placed in contact with film at room temperature. Test is performed after the dough was proofed to twice its original size. I'. Dough (no yeast) was placed in contact with film surface. refrigerated for 4 hours, then was allowed to reach room temperature before performing the test. J'. Dough (no yeast) was placed in contact with film surface. Test was performed after the dough was made. 86 Dough treatment had a definite impact on Wtforce values. For all three flours, proofed-yeast dough had less adhesion. Pastry flour doughes were less adhesive. With pastry doughes, Teflon had better release properties. The thass values also show better release for proofed-yeast dough systems. Pastry doughes had less adhesion. Dough release from Teflon was generally better than from PET and LDPE. The temperatures used to age the dough did not result in different adhesion strengths. 4.2.4 Wtforce/Itnass Results The effect of flour type, yeast, temperature, and film type on Wtforce and thass were studied. Analyses of variance results for the Wtforce and thass values are given in Table 13 and 14. All four factors had significant effect on thass. All factors, except for temperature, had significant effects on Wtforce. l as According to Tukey's Honestly Significant Difference test results for yeast conditions, there was no significant difference between contact-first-yeast and proof-first-yeast dough mean values (Appendix C, Table 25). There was no significant difference between Hi-protein and bread flour mean values (Appendix C, Table 26). When considering the flour factors, both were significantly different (p < 0.05) from pastry flour. According to the test results, the protein content may have an effect on the stickiness of the 87 Analysis of variance for Wtforce values of 3 different types of flours under three different yeast conditions at various temperature on 3 different films Table 13 Source of Degree of Sum of Mean F P variation freedom squares Square values Yeast (Y) 2 49930.570 24965.285 1587.6636 0.0000** Flour (F) 2 38076.142 19038.071 1210.7233 0.0000** YF 4 8661.255 2165.314 137.7028 0.0000** Replic (YF) 45 3911.319 86.918 5.5276 0.0000** Temp. (T) 1 51.229 51.229 3.2579 0.0778 YT 2 306.707 153.353 9.7525 0.0000** FT 2 136.557 68.278 4.3422 0.0189* YFT 4 177.790 44.448 2.8266 0.0356* Error 45 707.604 15.725 Film (M) 2 9373.635 4686.818 203.4749 0.0000** YM 4 886.085 221.521 9.6172 0.0000** FM 4 562.259 140.565 6.1025 0.0001** YFM 8 1065.557 133.195 5.7826 0.0000** TM 2 2.586 1.293 0.0561 YTM 4 167.499 41.875 1.8180 0.1273 FTM 4 7.269 1.817 0.0789 YFTM 8 172.960 21.620 0.9386 Error 180 4146.100 23.034 Total 323 represent p < 0.05 ** represent p < 0.01 88 Table 14 Analysis of variance for thass values of 3 different types of flours under three different yeast conditions at various temperature on 3 different films Source of Degree of Sum of Mean F Probability variation freedom squares Square values Yeast (Y) 2 5.787 2.894 352.2237 < 0.0000** Flour (F) 2 1.493 0.747 90.8741 < 0.0000** YF 4 2.124 0.531 64.6488 < 0.0000** Replic (YF) 45 0.277 0.006 0.7489 Temp. (T) 1 0.084 0.084 10.2407 < 0.0025** YT 2 0.057 0.029 3.4913 < 0.0389* FT 2 0.031 0.016 1.9105 > 0.1598 YFT 4 0.013 0.003 0.3841 Error 45 0.370 0.008 Film (M) 2 3.889 1.944 350.4445 < 0.0000** YM 4 1.479 0.370 66.6561 < 0.0000** FM 4 0.660 0.165 29.7597 < 0.0000** YFM 8 1.844 0.231 41.5487 < 0.0000** TM 2 0.035 0.017 3.1331 < 0.0460* YTM 4 0.047 0.012 2.1335 > 0.0785 FTM 4 0.012 0.003 0.5544 YFTM 8 0.039 0.005 0.8765 Error 180 0.999 0.006 Total 323 represent p < 0.05 represent p < 0.01 89 tested doughes. Noguchi (1976) suggested that dough stickiness correlated highly with the sulfhydryl content of the protein, but protein content itself did not correlate with adhesiveness. Protein content largely determines the grain's suitability for its intended end use. Yeast exists and is active in air as well as in the absence of air, but its behavior will change according to the environment (Vallery-Radot, 1957). In the presence of air, yeast grow rapidly and produce little alcohol, while in the absence of air, yeast growth is slow but alcohol formation is favored. During yeast fermentation, glycerol and succinic acid will also be produced, as well as carbon dioxide. Yeast provides flavoring compounds, affects the texture of dough and baked product, and creates carbon dioxide which decreases the density of the food (Matz, 1960). Carbon dioxide passes through the yeast cell wall as a dissolved compound, probably in the form of a bicarbonate ion. As the concentration of carbon dioxide increases in the free liquid outside the cell, gas bubbles begin to form around foci in the dough. The formation and migration of carbon dioxide in a network of cellular compartments, occupy about 120 cubic inches per pound of loaf, and serves to lighten or raise the dough. The physical properties of the dough are altered through the powerful stretching actions generated by diffusion and accumulation of carbon dioxide throughout the 9O dough mass. The effect of yeast condition on thass depended on the flour (F = 90.874, p = 0.000, Fig. 21). Pastry flour (with yeast) had higher mean values than bread flour (with yeast), perhaps because the cohesion forces within pastry flour is lower than the adhesion forces to films, so the remaining dough on the film will be higher. When there is no yeast in the dough, bread flour is most sticky. Tukey's Honestly Significant Difference Test result of thass (Fig. 22, Appendix C, Table 27) showed that the effect of yeast condition varied for different types of flours. For thass measures, values were highest when flours had no yeast. When flours had proof-first-yeast, both values were second highest. And when flour had contact-first-yeast, both values were the lowest. These differences appeared stronger for Hi-protein and bread flours. There was a highly significant (p < 0.01) difference between yeast condition and temperature for thass (F = 3.491, p = 0.0389) (Fig. 23). The effect of yeast condition depended on the effect of temperature for thass values. Mean values at refrigerated temperature were higher than those at room temperature for contact-first-yeast and no- yeast dough. Figure 23 shows that the proof-first-yeast dough at room temperature had higher values than those at refrigerated temperature. Tukey's Honestly Significant 9! \ - 111-non»; noun \\\\\ 05 ‘ new noun 5\ \ E3 mnv noun & \5: \ \ 5 5 5 5 \‘f _ ‘17"; 55‘ .. § 1 a1 PROOF-FIRST wT-naes (omen-em Han-21. TheWhIIuvdmedprod-flm. mummy-«16am mammmumm. .° N -°- I'll-stem + Ireed 4" Peem ooo 582. o b wr-me (salon-so) o I» 00‘ V T 0 ' f Contest-I'm: Proof-{Int No-yeaet Flouezz. TMIHSDteuWUmumnvduudprod-flm. contact-knew ' no-yeeetdmnghwhHI-ptotmbnedammm. \ E 0.3- n 3 é 0.2 - 0.1 - -°- Ne~yeeet + PreeHIreI + Contest-(Ire! 0 T Room Temp. FIgure24.Tuk uksHey' SDteetwumemeanveI velofme mmmamm ‘ no-yeeetdouohat manendteIrIgeI-etedtmun *_| RUN-TOMO- 93 Difference test results of thass indicated that the effect of yeast condition varied under different temperatures. However, within each yeast condition the effect of temperature was not significant (Fig. 24, Appendix C, Table 28). The effect of flour type on thass (F = 3.491, p = 0.0389) depended on temperature (Fig 25). Tukey's Honestly Significant Difference test results (Fig. 26, Appendix C, Table 29) showed how the effect of temperature condition varied for different types of flours. Higher values occurred for the flour at refrigerated temperature. These differences appeared stronger for Hi-protein and bread flours. When the dough was put in the refrigerator, the protein structure may have changed, and the low temperature will slow down the yeast fermentation. These factors may make the dough more sticky. A three-way interaction of yeast, flour, and temperature was not significant for thass. This three-way interaction is illustrated in Figures 27 and 28. Figure 27 shows that at room temperature, bread flour with no-yeast dough had the highest mean value, and pastry flour with contact-first-yeast dough had the lowest mean value. Figure 28 shows that bread flour with no-yeast dough had the highest mean value, and pastry flour with contact- first-yeast dough had the lowest mean value. For both room and refrigerated temperature, bread flour with proof-first— .. 5x5 ”:2 95 .0 O 1 - m-nnorem noun enno noun “““““““ ED metnv noun 5 5 I"P-illtss (GM/cu-sq, PROOF-FIRST CONTACT-FIRST Floumz7. ThewameevelueedHI-Welm breed.andpeetryIIouwlthproo(-flrst. mmwnomdmmmomza-qmmm. P ~4 - nn-nno'mn noun - enuo noun mm noun .0 O 1 79‘ 0 0.6 E 2 0.4 \55 . \\ § 0.3 . \‘f '3 .5 0.2« _ 0.1 a 555 'i " \W \\5 g3 \\\\5‘5 .. ..... 1 55 5\\\ 55555555; 5 PROOF-FIRM NO YEAST CON TAOT-F IRST Flunza mmwdeWvammwthmm 96 yeast was lower than contact-first-yeast dough. The mean value of pastry flour at room temperature was higher than flours at refrigerated temperature. The same situation occurred with Hi-protein and bread flour with proof-first- yeast dough. The Tukey's Honestly Significant Difference test results of thass values are listed in Appendix C, Table 30. The effect of film type on thass (F = 350.445, p =0.0000) was highly significant among all films. Tukey's Honestly Significant Difference test indicated that there was no significant difference between PE and PET film, but both films were significantly different (p < 0.05) from Teflon film (Appendix C, Table 31). This may be due to Teflon film's superior anti-stick/low friction properties (Dupont, 1988). The effect of yeast condition on thass varied for the different films (F = 350.445, p = 0.0000). The mean values of Teflon film were the lowest of all (Fig. 29). For both proof-first-yeast and contact-first-yeast dough, the mean values of PET film were higher than those of the PE films, but for no-yeast dough, the mean value of the PE film was higher than PET film. Tukey's Honestly Significant Difference test indicated that there was no significant difference between PE and PET film for proof-first—yeast and contact-first-yeast dough (Fig. 30, Appendix C, Table 32). For no-yeast dough, there was a significant difference 97 "T [:1 ten 0" ‘ “X I 55 5 5 \ 5 ‘ I V \( WT-Mhss (“fl/cu-80) \\\\\\5\\ ‘3‘. \ \ \5 5 ‘ “55‘“ L ‘ ">\'.\\\V\ \ I ~ ~ \ moor-runs? 0014111014,“, NO ““81 \5 §\ mam wmdmnuoammwno-mdoul onPE.PET..mmm .0 q —._ P! —+— PET + TEFLON .0 a .0 a. 9’ ;. WT-NASS (Galen-8°) O b 9 no Contact-(Int ProoI-flm No-yees FIoure30.T1key’eHSDteetWhmeemeenvduee0Iprod-Ilm.oanact and no-yeeetdoughonPE. PET,~and TEFLON flm. ' 98 between PE and PET film. PE film was slightly less sticky than PET film with yeast dough, however, with no-yeast, PE film was much more stickier than PET film. The interaction between flour and film was highly significant on thass (F = 29.760, p = 0.0000). The Teflon film had the lowest mean values of all. The mean value for the PET film was higher than the PE film (Fig. 31), and the mean value of PE film with bread flour was the highest. Tukey's Honestly Significant Difference test results of thass (Fig. 32, Appendix C, Table 33) indicates that there was no significant difference between Hi-protein and bread flour with PE or PET film, and no significant difference between Hi-protein and bread flour with Teflon film. There was no significant difference between PE and PET with the pastry flour. A three-way interaction of yeast, flour, and film was highly significant for thass (F = 41.549, p = 0.0000). This three-way interaction is illustrated in Figures 33, 34, and 35. Stickiness depended on yeast condition, flour, and type of film. Figure 33 shows that the mean values of proof-first- yeast dough on PET film were higher than those of PE and Teflon film for all three flours. Figure 34 shows that the mean value of contact—first—yeast on PET film was higher than those of PE film with bread and pastry flours, but with Hi-protein flour, the mean value of PE film was higher than - PE k\\\\\V PET . \ \ \ W031. ThernuevdueedHWbreed,mdpeflyIlwonPE, -PEr.endTEFLONIIm ;: 5' -»= a..- i \ 5 I'll-PROTEIN FLOUR BREAD FLOUR PASTRY FLOUR Hotness. TheWIeeevduedHI-proteln. breed.endpeeuyuouronPE. PET. and TEFLON Ilmwlh mouth-yeast dough. 0.3 - rs PET [I] 'rznon g 0.25“ g 0.2 i; 5 g 0.15 0; 5 \\\\\5\ I'll-PROTEIN FLOUR BREAD FLOUR PASTRY FLOUR FIowe34.111e\AMueveIue0fHI—protdn.bned.andpeetryflouonPE. PET. and TEFLON Ilmwlth canted-flut-yeeet dough. ’ N " ‘9 ‘9 V. 94 o ._ ‘ ‘2 ’ IL >. m p. ‘2 O. dereed,andpeetryMonPE.PET.andTEFLONflmwlh . Thewmeeevdue I‘D-MM - Flawless. 102 PET film. Teflon film with pastry flour had the lowest mean value of all. Figure 35 shows that for all three flours, the mean values of PE film were higher than the mean values of PET film. These differences appeared stronger for bread flour. Tukey's Honestly Significant Difference test results of thass values are listed in Appendix C, Table 34. The interaction between temperature and film type was significant (F = 3.133, p = 0.0460) for thass (Fig. 36). Under refrigerated temperature, thass values were higher than those at room temperature. Tukey's Honestly Significant Difference test indicated that Teflon film was less sticky than both PE and PET film. Temperature had no effect on all three films for thass (Fig. 37, Appendix C, Table 35). The flour samples used were Hi-protein, bread, and pastry flour. According to the manufacturing company (General Mill, Inc., 1991), Hi-protein flour was milled from a hard spring wheat, bread flour was milled from hard winter wheat, and pastry flour was milled from hard and soft winter wheat blend. Hard wheat is physically hard, and has relatively high protein content. The hardness is under genetic control and is thought to result from the strength of the bonding between the protein and starch in the endosperm (Hoseney, 1978). Bonding between protein and starch is weak for soft wheat. Soft wheat is low in protein. Also, dough from a Home 37. Tukey's HSD test Wtrnass mean values at room and refrigerated tempetature dough wIth PE. PET. and TEFLON flm. 104 high protein flour will have less mobility or greater stiffness than from a low protein flour with the same percentage of absorption. This may explain why the different types of flour react differently. ntgoroe According to Tukey's Honestly Significant Difference test results, there was no significant difference between proof-first-yeast and no-yeast dough for Wtforce values (Appendix C, Table 36). There was a significant difference (p < 0.05) between Hi-protein, bread, and pastry flour for Wtforce values (Appendix C, Table 37). The effect of yeast condition depended on the flour type for Wtforce (F = 137.703, p = 0.000, Fig. 38). Contact-first-yeast dough had lower Wtforce mean values than proof-first-yeast dough. Pastry flour had the lowest mean values among all flours, bread flour was most sticky. Tukey's Honestly Significant Difference Test result of Wtforce (Fig. 39, Appendix C, Table 38) showed that the effect of yeast condition varied for different type flours. Values were highest when flours had no yeast. When flours had proof-first-yeast, both measures (thass and Wtforce) were second highest. And when flour had contact-first- yeast, both measures had the lowest values. These differences appeared stronger for Hi-protein and bread flours. All gluten proteins contain disulfide groups, each “33"”) on o N o o o ‘: I \I / w'r-ronce (011 N I“ § 0 Floureae. TheWIIoroevelueeofHI-pmteln.breed.andpeetryflourwlth proof-first. cannot-0m. and no-yeeetdough. ./ 70 "— Hl-pmteln -+" Breed 4" Pantry [ “ 00 - 5 1"" 5 so - P . G ' ‘1 4° _. g 30 - l E 20 : " 10 fl/ CCCCCCCCC ProoI-Ilret No-yeefl Home 39. Tukey's HSD test Wtforce mean values of HI-protein. breed and pastry _ flour with prod-first. contact-first, and no-yeeet dough. 106 polypeptide chain has an average of two (Wall, 1967). Although gliadin and glutenin proteins possess similar amino acids, their physical behaviors differ; hydrated gliadin is a viscous mass, whereas hydrated glutenin is cohesive and elastic. In the hydration stage during dough formation, water penetrates the protein particles and associated with polar sites, overcomes forces that cause the molecules to adhere. Some of the protein molecules may be cleaved at the disulfide bonds and reassembled by oxidation to conform more effectively to the mixing stress. During proofing, the protein matrix is stretched. The ability to stretch depends upon the elastic characteristics of the gluten protein. Yeast brings about changes in the dough in the course of fermentation. This includes depletion of fermentable substances, accumulation of waste products in the form of carbon dioxide, alcohols, acids and esters, modification of pH conditions, and a softening or mellowing of the gluten character (Pyler, 1978). According to Jackel (1969), yeast requires about 45 min in a favorable environment to attain full adaptation to fermentation. Proteolytic enzymes act upon the protein materials of the dough, the overall effect of these enzymatic reactions is a softening of the dough, due in part to a reduction in the absorption capacity of the starch material, and in part to a weakening of the gluten system. There was a highly significant (p < 0.01) difference 107 between yeast condition and temperature for Wtforce (F = 9.753, p = 0.0003, Fig. 40). The effect of yeast condition depended on the effect of temperature for Wtforce values. Mean values at refrigerated temperature were higher than those at room temperature for contact-first-yeast dough. Figure 40 shows that the mean values of proof-first-yeast dough at room temperature were higher than those at refrigerated temperature. No-yeast dough showed higher values at room temperature than at refrigerated temperature. Tukey's Honestly Significant Difference test results of Wtforce indicated that the effect of yeast condition varied under different temperatures. However, within each yeast condition the effect of temperature was not significant (Fig 41, Appendix C, Table 39). The effect of flour on Wtforce (F = 4.342, p = 0.0189) depended on temperature (Fig 42, 43, Appendix C, Table 40). Higher Wtforce mean values occurred for flour at refrigerated temperature. These differences appeared stronger for Hi-protein and bread flours. A three-way interaction of yeast, flour, and temperature was significantly different (F = 3.491, p = 0.0356) for Wtforce. This three-way interaction is illustrated in Figure 44, 45, and Appendix C Table 41. Figure 44 shows that at room temperature, pastry flour with contact-first-yeast dough had the lowest mean value. Except for bread and pastry flour with proof-first-yeast and no- - noon TE n. m'C) nsrm. 're p \ dmnhetroomammedtempemure 3 41. Tukey's HSD test Wtfowe mean values of proof-first, contact-first and no-yeeet dough at room and remgenmd temperature. /s .5 5 5 \ I'll-PROTEIN F R ER FIgure42. TheWfloree ueeoIHI-ptueh.breed.andpeeuynwrdwgh almanaMreflIgeratedtempetmne. Home 43. Tukey’s HSD test Wtforce mean values of HI-proteIn. breed. and paetryflouret roomand reI‘rIgerated temperature. 110 yeast dough, the Wtforce values at refrigerated temperature were higher than those at room temperature. The effect of film type on Wtforce (F = 203.475, p = 0.0000) was highly significant among all films. Tukey's Honestly Significant Difference test indicated that there was no significant difference between PE and PET film, but both films were significantly different (p < 0.05) from Teflon film (Appendix C, Table 42). The effect of yeast varied for the different films for Wtforce (F = 203.475, p = 0.0000, Fig. 46). The mean values for the Teflon film were the lowest of all. For the contact-first-yeast, the mean value of the PET film was higher than that of the PE film. Tukey's Honestly Significant Difference test indicated that there was no significant difference between PE and PET film for proof-first-yeast and contact-first-yeast dough (Fig. 47, Appendix C, Table 43). For no-yeast dough, there was no significant difference between PE and PET film. PE film was slightly less sticky than PET film with yeast dough, however, with no-yeast, PE film was much more sticky than PET film. The interaction between flour and film was highly significant on Wtforce (F = 9.617, p = 0.0000). The Teflon film had the lowest mean values of all. For both Hi-protein and bread flour, the mean values of PE and PET film were close (Fig. 48), while the mean value of Teflon was lower. arr-tone: (cu/cu-sg) 3 3 ‘8 3 8 3 3 FIgureu. TheMorceveIueedHI-proteh. breed,endpeetlymmproof-fira. corned-firstand no-yeeetdouohat room (23°C) temperature. TRY LOUR 5 5 55 5 PROOF-F CONTACT-FIRST no vans? // / Floure45. TheWtforeevelueedHI-proteln.breed.andpaeu'yflwwmproot-flret, - cornea-fire!“ no—yeaetdouohat relflgerated (4°C) temperature. n \ I; 20- '10 CON TTAO-F IRST NO YEAST Flore“. TheWtIoroeveIueeof prod-fitnoorwed-flMeMno-yeaetdough onPE PET andTEFL . WT-PORCI (GM/cn-eo) 0 o o 3 8 3 S 8 1w Al I l l ‘0 "I 1 '0 IR Id -I «‘2 .4 II ‘I r- O 2 FIgure47. Tukey'eH ‘SDt tEofeaWtforcemnveluee dprfiqd-flmwm first. amino-yeast dPEoughon PET,andTEFL 113 Pastry flour - film interactions were the lowest. Tukey's Honestly Significant Difference test results (Fig. 49, Appendix C, Table 44) indicates that there were no significant differences for Hi-protein and bread flour with either PE or PET film, and no significant differences between Hi-protein and bread flour for Teflon film. There was no significant difference between PE and PET film for pastry flour. A three-way interaction of yeast, flour, and film was highly significant for Wtforce (F = 5.783, p = 0.0000). This three-way interaction is illustrated in Figure 50, 51, and 52. Stickiness depended on yeast condition, flour, and type of film. Figure 50 shows that the mean values of proof-first yeast dough on PET film were higher than those of PE film with Hi-protein and bread flours. Figure 51 shows that the mean value of contact-first-yeast on PET film was higher than those of PE film for all three flours. Teflon film with pastry flour had the lowest Wtforce value of all. Figure 52 (Appendix C, Table 45) shows that for no- yeast dough the mean value of PE film with bread flour was the highest, and the Teflon film with pastry flour the lowest. For both Hi-protein and bread flour, the mean value of PE film was higher than that of PET film. For pastry flour, the mean value of PET film was higher than PE film. The interaction between temperature and film on Wtforce "4 \ \' I'll-P 0U PASTR FL % 4: / / 3.3.: A 1.4 ,_ O 2 WT-PORC // 5 A FLOUR BREAD FL R Home. TheVWoroevdueeolHI—proteh,breed.endpestryllwonPE. PET.andTEFLONIIm. o — F 30 " 20 1 10 " ’ —~— PE -+— PET + TEFLON 0 r HI—pfmdn w-r-roncz (cu/cu-sg) ‘ Figure 49. Tukey's HSD test Wtforce meen values 0! Hl-proteln. breed. and pastry Ilour on PE. PET, and TEFLON Ilrn. "5 \\ FIgure50.1110thoroevdueolHI—pr0teh.hreed.andpestryfiouonPE. PET. and TEFLON llm wlth prud-fiet—yeeet dough. wT-ronca (on/cu-ep) .e d R? R3 \- t t . i \\\\ I'll-PROTEIN FLOUR BREAD FLOUR PASTRY FLOUR FI9ure51. TheWtIoroevelueotHI-proteln. breed.and pastryllouron PE, PET. and TEFLON flm wlth contact-first-yeaet dough. O _l U. LU '— [LI 0. \\ g “mm Marco vuue of HI—proteln. breed. and pastry flour on PE, PET, and TEFLON 117 was not significant (Fig. 53). For doughes at refrigerated temperature, mean values were higher than those at room temperature. Tukey's Honestly Significant Difference test indicated that Teflon film was less sticky than both PE and PET film. Temperature had no effect on any of the three films (Fig. 54, Appendix C, Table 46). In the original study, we reported force per unit area at separation which implies that force is proportional to the contact area between the film and the dough. In a separate study, this hypothesis was tested by incorporating various lengths and widths of the film. Doubling the width of the film and leaving the same length increased the force by 1.75 times instead of two times as expected. Doubling the length of the film and leaving the same width only increased the force 1.2 times instead of two times as expected. Therefore, force is not proportional to area, nor is it proportional to length or width of the film. Therefore, in future studies, only the force of a given standardized opening should be reported. CONCLUSIONS This study was designed to: 1. Evaluate a device for determining adhesion between refrigerated dough and the contacting surface, and 2. To determine the influence of flour type, yeast condition, and temperature on adhesion between dough and plastic films. The major findings of the study are summarized below: (1) Phase I Study: Wettability Test A. Wettability was characterized using the inclined plane method, and the results show that PETG had the highest angle and Teflon had the lowest angle. Stickiforce Meter Test B. Proof-first-yeast dough on PETG film at 4°C had the highest thass mean value, and contact-first-yeast dough on Teflon film at 23°C had the lowest thass mean value. As for the Wtforce mean values, proof-first-yeast dough on film 78698 at 4°C had the highest mean value, and contact-first- yeast dough on Teflon film at 4°C had the lowest. thass PETG was found to be the most adhesive material, and 119 120 Tri-extruded PE found to be the least adhesive material. When we consider both film and yeast factors, PETG with proof-first-yeast dough remained the most adhesive interaction, and HDPE with contact-first-yeast dough was found to be the least adhesive. Considering various films and the different temperatures, PETG at 4°C proved to be the most adhesive, and Teflon at 23°C was found to be the least. With all three factors combined, PETG with proof-first-yeast dough at 4°C was found to be the most adhesive material, and Teflon with contact-first-yeast dough at 23°C was found to be the least adhesive. Wtforge The Wtforce values of Silicone release paper are a result of that material requiring the highest amount of water to break away the test film from the dough surface. Teflon film used the least amount of water. When type of film and the yeast factor are considered, film 78G98 with proof-first-yeast dough was found to be the material that required the greatest force, and Teflon film the least. If we combine film type with the temperature factor, Silicone release paper at 4°C required the most force and Teflon at 4°C required the least. When we combine all three factors together, film 78098 with proof-first-yeast dough at 4°C was found to be the material that used the highest amount of water to break the test film away from the dough surface, 0 O and the Teflon film with contact-flrst-yeast dough at 4 C 121 used least amount of water. Each factor contributed to and affected the dough stickiness. 1W: Wettability Test A. The results from performing the Inclined plane method show that PET had the highest angle, and Teflon had the lowest angle. stickiforce Meter Test B. Bread flour with no-yeast dough on PE film at 4°C had the highest thass mean value, and pastry flour with no- yeast dough on Teflon film at 23°C had the lowest thass mean value. As for the Wtforce mean values, bread flour with no-yeast dough on PE film at 23°C had the highest mean value, and pastry flour with contact-first-yeast dough on Teflon film at 4°C had the lowest. thasg PE film found to be the most adhesive material, and Teflon film found to be the least adhesive material. Bread flour had the highest adhesive property, and pastry flour had the lowest. When yeast conditions are combined with the flour factor, bread flour with no-yeast dough had the highest adhesiveness, and pastry flour with contact-first- yeast dough had the lowest. Considering yeast conditions, flour factor and temperature factor together, bread flour with no-yeast dough at 4°C had the highest adhesiveness, and pastry flour with contact-first-yeast dough at 23°C had the 122 lowest. Combine the four factors (Yeast, flour, temperature, and film) together, bread flour with no-yeast dough at 4°C on PE film was the most adhesive, and pastry flour with contact-first-yeast dough on Teflon film at 4°C was the least adhesive. litters; The Wtforce mean values showed that PE film was the material that used the most force to break the test film away from the dough surface and Teflon film the least. Considering both film and yeast factors, PE film with no- yeast dough used the highest amount of water to break away from the film, and Teflon film with contact-first-yeast dough the least. When film type and flour factors are considered, Hi-protein flour with PE film required the most force, and pastry flour with Teflon film required the lowest. Considering film type with yeast and flour factors, bread flour with no-yeast dough on PE film required the highest amount of water, and pastry flour with contact- first-yeast dough on Teflon film the least. Looking at the mean values of film types, and both flour and temperature factors, Hi-protein flour on PE film at 4°C found was the highest, and pastry flour on Teflon film at 23°C the lowest. Combining all factors, bread flour with no-yeast dough on PE film at 23°C was the combination that used the highest amount of water to break the test film away from the dough surface, and pastry flour with contact-first-yeast dough on 123 Teflon at 4°C was the combination that used the least. (3) PVC, PET, and PETG all have a polar surface. That may be one reason why these three films stuck to the dough more than the other materials. The use of release agents, added as resins or used as coatings applied to a solid, may prevent/decrease adhesion of another solid. Hwoever, the silicone-based materials did not provide the required release properties. This was true in all cases. (4) Good correlation was observed between the Wtforce (gram-force) and thass (gram-mass) results. R3 = 0.80 for Phase I study, and R2 = 0.92 for Phase II study. (5) Yeast provides flavoring compounds, affects the texture of dough, and creates carbon dioxide. The physical properties of the dough are altered through the powerful stretching actions generated by diffusion and accumulation of carbon dioxide throughout the dough mass, and the web structure reveals that thin-walled gluten strands offer minimum resistance to stretching when pulled. This might explain why yeast dough was less sticky than no-yeast dough. (6) Hard wheat has relatively high protein content. Greater stickiness of this type of dough is thought to result from the strength of the bonding between the protein and starch in the endosperm. The high protein dough has less mobility and greater stiffness. Bonding between protein and starch is weak for soft wheat, which usually is low in protein content. This may explain why different 124 types of flour reacted differently in the tests performed. (7) The original hypothesis that the force is required for separation is proportional to the contact area between the film and the dough was proven false by testing various lengths and widths of film. Doubling the width and length of the film increases the force by only 1.75 and 1.2 times respectively, rather than the expected 2 times. RECOMMENDATIONS The instrumental technique using a Stickiforce Meter appears useful for measuring dough stickiness. The following are recommendations for future research: 1. The testing results obtained from a Farinograph will differ if test factors are strictly controlled. The variation of dough development will change the mixing tolerance index. Normally, relative humidity and temperature are controlled factors when using a Farinograph. When the experiment environment changes, the instrument changes, and results will vary considerably if there is no viable control. 2. Standardize the test conditions to obtain meaningful comparisons, which requires selection and control of temperature, relative humidity, and fermentation time. 3. The use of commercial flour instead of the pure variety did not enable us to differentiate what kind of protein and starch are in the flour. We need to do more chemical compound testing to obtain the ingredient analysis of each flour type: That is, the percentage of each component of protein and starch, in order to do a more comprehensive study on the cause of stickiness in dough. 125 APPENDICES APPENDIX A 126 APPENDIX A Absorption at 14% moisture content BtM A-86 100-M_14 Pastry Bread Hi-protein Flour Flour Flour M : Flour Moisture 9.38% 9.27% 9.08% A : Absorption 14% mb B : Absorption, as-is mb Héo Added 29.52 ml 32.65 ml 33.20 ml Flour Weight 50.48 g 47.50 g 46.80 g Pastry Flour ._100x29.52_58'48% B 50.48 58.48.~9.38_14_50_4 A'86x loo-9.38 Bread‘Flour _100x32.5_68.4% B 47.5 58'4+9'27-14-59.62 A'86x'100-9.27 Hi-protein Flour _100x33.2_70.94% B 46.8 70.94+9 '08-14-61.69 A'sax 100-9.08 APPENDIX B 127 Appendix B Tukey's Honestly Significant Difference Test of Wtforce and thass Results for Phase I Study Table 15. thass mean values of the test materials. Film Type Mean1 PETG 4.7 x 10'2“ ISC-60 3.5 x 10'2a 78098 2.8 x 10-2a pvc 2.8 x 10‘2‘1 SILICONE PAPER 2.4 x 10‘2“ HDPE 1.9 x 10'2“ PET 1.2 x 10'2“ 80C146A 6.6 x 10‘3“ 2% EVA/VEG OIL 3.3 x 10'3“ KRAYTON 1.2 x 10’ a 2% EVA/MYV 9-40 8.2 x 10:: 2% EVA/1.5% PAM 7.5 x 104‘ TEFLON FEP 7.2 x 104‘ TRI-EXTRUDED PE 6.7 x 10 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 128 Table 16. thass mean values of the test materials with proof-first and contact-first yeast dough. Treatment Mean PETG/Proof-first 9.2 x 10'2“-1 ISC-60/Proof—first 6.4 x 10'2“ PVC/Proof-first 5.2 x 10‘2a SILICONE/Proof—first 4.4 x 10'2“ 78698/Proof—first 4.3 x 10'“ HDPE/Proof-first 3.7 x 10'2“ PET/Proof-first 2.3 x 10‘2“ 78698/Contact-first 1.4 x 10‘2‘3 80C146A/Proof-first 8.5 x 10'3“ EVA/OIL//Proof-first 5.8 x 10'3‘51 ISC-60/Contact-first 5.3 x 10'3“ 80C146/Contact-first 4.6 x 10'3‘a PVC/Contact-first 3.9 x 10'3‘a SILICONE/Contact-first 3.7 x 10:3“ KRAYTON/Proof-first 1.5 x 10_3a PETG/Contact-first 1.4 x 10_3a PET/Contact-first 1.3 x 10_3a EVA/PAM/Proof—first 1.1 x 104: EVA/MYV/Proof-first 9.9 x 10-48 TEFLON/Proof-first 9.5 x 104”l KRAYTON/Contact-first 9.3 x 10_4a EVA/OIL/Contact-first 7.4 x 10__4a TRI/PE/lProof-first 7.1 x 10_4a EVA/MYV/Contact-first 6.5 x 10_¢a TRI/PE/Contact-first 6.3 x 10%a TEFLON/Contact-first 5.0 x 10_4a EVA/PAM/Contact-first 4.5 x 10_4a HDPE/Contact-first 4.0 x 10 ----- 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 129 Table 17. thass mean values of the test materials at room (23°C) and refrigerated (4°C) temperature. Treatment Mean PETG/Refri 9.2 x 10'2“ ISC-GO/Refri 6.5 x 10'1“"l PVC/Refri 5.5 x 10'1’‘3 78698/Refri 5.1 x 10‘2“ SILICONE/Refri 4.5 x 10'2“ HDPE/Refri 3.6 x 10"2a PET/Refri 2.3 x 10‘2“ 80C146A/Refri 1.1 x 10'2a EVA/OIL/Refri 6.2 x 10'3“ 78G98/Room 5.2 x 10'3:! ISC-60/Room 3.8 x 10'3“ SILICONE/Room 2.8 x 10'?3‘ 80C146A/Room 2.5 x 10:3a KRAYTONE/Refri 1.7 x 10_3ll EVA/MYV/Refri 1.3 x 10_3a TEFLON/Refri 1.2 x 10 33 PET/Room 1.1 x 10:3‘a HDPE/Room 1.0 x 10_3: PETG/Room 1.0 x 10_¢a EVA/PAM/Refri 9.2 x 10%a TRI/PE/Refri 8.7 x 10_4a PVC/Room. 7.8 x 10_4a KRAYTON/Room 7.0 x 10_¢a EVA/PAM/Room 5.8 x 10-4a TRI/PE/Room 4.6 x 10_¢a EVA/OIL/Room 4.2 x 104‘a EVA/MYV/Room 3.5 x 1043 TEFLON/Room 2-5 X 10 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test "WLL " M 130 Table 18. thass mean values of proof-first and contact- first yeast dough at room (23°C) and refrigerated (4°C) temperature. Treatment Mean1 Proof/Refri 5.2 x 10'2“ Contact/Refri 4.3 x 10‘2‘ Proof/Room 2.9 x 10‘:3 Contact/Room 1.1 x 10"'1 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 131 Table 19. thass mean values of the test materials with proof-first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature. PETG/Proof-first/Refri ISC-60/Proof-first/Refri PVC/Proof-first/Refri SILICONE/Proof-first/Refri 78G98/Proof—first/Refri HDPE/Proof-first/Refri PET/Proof-first/Refri 78698/Contact-first/Refri 80C146A/Proof-first/Refri EVA/OIL/Proof-first/Refri ISC-60/Contact-first/Refri PVC/Contact-first/Refri 78698/Proof-first/Room 80C146A/Contact-first/Refri ISC-60/Proof-first/Room SILICONE/Contact-first/Refri SILICONE/Proof-first/Room 78698/Contact-first/Room ISO-60/Contact-first/Room 80C146A/Contact-first/Room 80C146A/Proof-first/Room KRAYTON/Proof-first/Refri SILICONE/Contact-first/Room PETG/Contact-first/Refri PET/Contact-first/Refri TEFLON/Proof-first/Refr HDPE/Proof-first/Room EVA/MYV]Proof-first/Refri KRAYTON/Contact-first/Refri EVA/OIL/Contact-first/Refri EVA/PAM/Proof-first/Refri PET/Proof-first/Room . EVA/MYV/Contact-first/Refr1 PETG/Contact-first/Room PET/Contact-first/Room EVA/PVM/Proof-first/Room PVC/Proof-first/Room . TRI/PE/Proof—first/Refri PETG/Proof—first/Room KRAYTON/Proof—first/Room TRI/PE/Contact-first/Refri TEFLON/Contact-first/Refri. EVA/PAM]Contact-first/Refri PVC/Contact-first/Room omwwowwOOHt-H-IHt—Imonumental:L§LGG$GEBBBE¢§LG$G§EGB§E xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx H O I w 0' mmmmmmml‘HHI—‘Hl—‘HHHHHHHHNNNNNUUkmO‘mQQHHN-fiQQQHI-‘H 132 Table 19: (cont'd) Treatment Mean1 EVA/OIL/Proof-first/Room 5.7 x 10"“3 KRAYTON/Contact-first/Room 5.6 x 10'“° HDPE/Contact-first/Room 5.0 x 10'“° TRI/PE/Proof-first/Room 5.0 x 10”“’ EVA/MYV/Proof-first/Room 4.8 x 10"413 TRI/PE/Contact-first/Room 4.3 x 10'413 TEFLON/Proof—first/Room 3.3 x 10‘“’ HDPE/Contact-first/Refri 3.1 x 10‘“’ EVA/OIL]Contact-first/Room 2.6 x 10"“3 EVA/MYV/Contact-first/Refri 2.2 x 107“” EVA/PAM/Contact-first/Room 2.1 x 10'"413 TEFLON/Contact-first/Room 1.7 x 10'413 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 20. Wtforce mean values of the test materials. Film Type Mean _ _______________________________________________ ;__ SILICONE PAPER 18.19a 78G98 16.27ab Isc-eo 14.20am 80C146A 12 . 805cc PETG 10.22b d PET 8.86 c e pvc 8.40%“? HDPE 7.09;; 2% EVA/VEG OIL 6.28def KRAYTON 131-22“ 2% EVA/1.5% PAM 3.359f TRI-EXTRUDED PE 3'04“ 2% EVA/MYV 9-60 2-75f TEFLON FEP 1 means followed by the same letters are no different at p < 0.05 by Tukey's HSD Test t significantly at 133 Table 21. Wtforce mean values of the test materials with proof-first and contact-first yeast dough. Treatment Mean 78698/Proof-first 20.80a SILICONE /Proof-first 19 . 62*511D ISC-60/Proof-first 18 . 03"” SILICONE [Contact-first 16 . 75abcd PETG/Proof-first 15 . 92‘1”“ 80C146A/Proof-first 13 . “bed“ PET/Proof-first 12 . 43¢def PVC/Proof-first 12 . 3 6"def 80C146A/Contact-first 12 . 16Cdef 78698 [Contact-first 11 . 73°d°f9 ISO—60 / Contact-f irst 10 . 3 Gdefgh HDPE/Proof—first 9 . 33°f‘3hi EVA/OIL/Proof-first 7 . 64‘3” KRAYTON/Proof-first 5 . 4 39hij PET/Contact-first 5.29;j EVA/OIL/Contact-first 4 . 91hij HDPE/Contact-first 4.86Mj PETG/Contact-first 4.52hig PVC/Contact-first 4.44hij EVA/PAM/Proof-first 4'321j KRAYTON/Contact-first 3.64ij EVA/MYV/Proof—first 3°601j TRI/PE/Proof—first 3.59ij EVA/PAM/Contact-first 3.40ij TEFLON/Proof-first 3.16ij TRI/PE/Contact-first 3.12j EVA/MYV/Contact-first 2.48j TEFLON/Contact-first 2.34 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 22. Wtforce mean values of the test material at room (23°C) and refrigerated (4°C) temperature. SLICONE/Refri 78698/Refri ISC-GO/Refri 80C146A/Refri PETG/Refri PVC/Refri PET/Refri SILICONE/Room 78698/Room HDPE/Refri ISC-60/Room EVA/OIL/Refri 80C146A/Room KRAYTON/Refri PETG/Room PET/Room EVA/PAM/Refri PVC/Room TRI/PE/Refri KRAYTON/Room EVA/PAM/Room HDPE/Room EVA/OIL/Room EVA/MYV/Refri TRI/PE/Room TEFLON/Room EVA/MYV/Room 10.79d9f9 E. 10 . 19d“?h ' 9 . 169fghi 9 . ()ngth 5.48f9hi 5.35ghi 4.96ghi 4.23ghi 3.86hi 3.67hi 3.591 3.501 3.401 3.391 3.261 3.041 2.921 2.821 2.591 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 135 Table 23. Wtforce mean values of proof-first and contact- first yeast dough at room (23°C) and refrigerated (4°C) temperature. Treatment Mean1 Proof/Refri 14.99a Contact/Refri 7.75” Proof/Room 6.39” Contact/Room 5.11” 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test n- P‘I-I I 136 Table 24. Wtforce mean values of the test materials with proof-first and contact-first yeast dough at room (23°C) and refrigerated (4°C) temperature. Treatment Mean 78698/Proof—first/Refri 28.19a PETG/Proof-first/Refri 25.89“” SILICONE /Proof-f irst/Refri 24 . 99” ISC-60/Proof-first/Refri 23 . 89"”:d SILICONE / Contact-f irst / Refri 22 . 83:”d PVC/Proof-first/Refri 21.211) 2’ : PET/Proof-first/Refri 19.13 S : 80C146A/Proof-first/Refri 16.60: i 9 80C146A/Contact-first/Refri 16.44 i : HDPE/Proof-first/Refri 15 . 0729111 SILICONE/Proof-first/Room 14.25: :13 78698/Proof-first/Room 13 . 42159hijk 78698/Contact-first/Refri. i: - ggfghijk ISC-60/Contact—f1rst/Refr1 1218fghijkl ISC-60/Proof-first/Room . EVA/OIL/Proof-first/Refr1 SILICONE]Contact-first/Room 10 .68ghijklmn 78698/Contact-first/Room 80C146A/Proof-first/Room 10. soghijklmno 8 ozohijklmnopq lSC-60 / Contact- -f irst/ Room ° hij klmopq 80C14 6A/ Contact- -f 1rst / Room 7 . 89ijklmnopq ICRAYTON/ Proof-f1rst/Refr1 7 . lSjklmnopq EVA/OIL/Contact-f1rst/Refr1 6 . 84jklmnopq HDPE/ Contact-f1rst/Refr1 6 . Sljklmnopq PET / Contact- -f 1rst / Ref r1 6 . 4 oklmnopq PETG / Proof— -f irst / Room 5 . 94km“)pq PET/ Proof- f1rst / Room 5 . 741111;:qu EVA/PAM/Proof- -first/Refri 5. 04mnopq PETG / Contact-f irst / Room 4 . 7 6mopq PVC / Contact-f 1rst / Refri 4 . 68mnopq PETG] Contact-f irst / Ref r1 4 ' 2 ”man PVC / Contact-f first / Room 4 ° 2 (1),”,qu EVA/MYV/Proof- -first/Refri 2 ismopq PET / Contact-f irst / Room 4 ° 0 znopq TRI/PE/Proof— -first/Refri 3 ' 81mm EVA / OIL/ Proof -f irst / Room 3 ' 8 0’1qu KRAYTON/ Contact-f1rst/Refr1 3 ° 70mm KRAYTON/ Proof— -f irst / Room 3 ° 6 0”qu EVA/PAM/Proof-first/Room 3 ° 59mm HDPE/ Proof— -f irst/ Room 3 ° 5 1mm PVC / Proof —f irst / Room 3 ' 48mm KRAYTON/ Contact-f irst / Room 3 ' 4 2mm EVA/ PAM/ Contact-f1rst/Refr1 3 39mm EVA/ PAM/ Contact-f irst / Room 137 Table 24: (Cont'd) TRI[PE/Contact-first/Refri TEFLON/Proof-first/Room HDPE/Contact-first/Room TRI/PE/Proof-first/Room TEFLON/Proof-first/Refri EVA/MYV/Proof—first/Room EVA/OIL/Contact-first/Room TRI[PE/Contact-first/Room EVA/MYV/Contact-first/Room TEFLON]Contact-first/Room EVA/MYV]Contact-first/Refri TEFLON/Contact-first/Refri 1 means followed by the same letters are different at p < 0.05 by Tukey's HSD Test not significantly APPENDIX C 138 APPENDIX C Tukey's Honestly Significant Difference Test for Wtforce and thass Results for Phase II Study Table 25. thass mean values of proof-first, contact- first, and no-yeast dough. 1 _Yeast Type ___________________________ Mean ____________ 3 None 4 . 3 x 10': ; Proof-first 1.8 x 10_n3 Contact-first 1.3 x 10 n 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test Table 26. thass mean values of Hi-protein, bread, and pastry flour. Flour Type -EEEE ....... --------------------------------------------- -1a . 2.9 x 10 H1-protein 1 5 x 10-11, Pastry ' 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 139 Table 27. thass mean values of proof-first, contact-first, and no-yeast dough with Hi-protein, bread, and pastry flour. Treatment Mean1 None/Bread 6.3 x 10‘1‘El None/Hiprotein 4.6 x 10'“’ Proof/Hiprotein 2.5 x 10’“: None/Pastry 2.1 x 10'“: Proof/Pastry 1.8 x 10"led Contact/Hiprotein 1.8 x 10'lcd Contact/Bread 1.4 x 10’1”: Proof/Bread 1.2 X 10:23 Contact/Pastry 6.5 x 10 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 28. thass mean values of room (23°C) and refrigerated (4 ° C) temperature with proof -f irst , contact-f irst , and no-yeast dough. Treatment Mean1 ------- None [Refri 4 . 5 x 10:: None/Room 4.1 x 10_n3 Proof-first/Room 1.9 x 10_n3 Proof-first/Refri 1.8 x 10_n) Contact-first/Refri 1.6 x 10_2b 9.6 x 10 Contact-first/Room 1 means followed by the same letter are n different at p < 0.05 by Tukey's HSD Test at significantly __13 140 Table 29. thass mean values of room (23°C) and refrigerated (4°C) temperature with Hi-protein, bread, and pastry flour. Treatment Mean Bread/Refri 3.2 x 10’1“ Hiprotein/Refri 3.1 x 10'1“ Hiprotein/Room 2.7 x 10’1“” Bread/Room 2.7 x 10'1“” Pastry/Refri 1.8 x 10'1b Pastry/Room 1.5 x 10'1” 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 30. thass mean values of proof-first, contact- first, and no-yeast dough with Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature. Treatment Mean Bread/None/Refri 6.6 x 103:1, Bread/None/Room 6.0 x 10_1bc Hiprotein/None/Refri 4.9 x 10_n: Hiprotein/None/Room 4.3 x 10_1d Hiprotein/Proof/Refri 2.5 x 10_1de Hiprotein/Proof/Room 2.4 x lo—ldef Pastry/None/Refri 2.2 x 10-1defg Pastry/None/Room 2.1 x -1de f9 Hiprotein/Contact/Refri 2.0 x -1defg Bread/Contact/Refri 1.9 x 10_1defg Pastry/Proof/Room 1.8 x _ 1defg Pastry/Proof/Refri 1.7 x 10_mefg Hiprotein/Contact/Room 1.5 x 10_1defg Bread/Proof/Room 1.3 x -1defg Bread/Proof/Refri 1.2 x -2efg Bread/Contact/Room 8.8 x 10_zfg Pastry/Contact/Refri 7.7 x 10__29 Pastry/Contact/Room 5.3 x 10 ___________ 1 means followed by different at p < 0.05 by Tukey's HSD Test Fr“ I‘m—4m 141 Table 31. thass mean values of PE, PET, and TEFLON film. Film Type Mean1 p15: 3.5 x 10'1“ PET 3.0 x 10'1“ TEFLON 9.5 x 10'” 1 means followed by the same letter are not significantly [ different at p < 0.05 by Tukey's HSD Test i -1'1' Table 32. thass mean values of proof-first, contact- first, and no-yeast dough on PE, PET, and TEFLON film. Treatment Mean1 None/PE 6.6 X 10:55 None/PET 4.1 x 10_11m Proof-first/PET 3.1 x lo-lcd None/TEFLON 2.3 x 10_led Proof-first/PE 2.2 x 10_1cd Contact-first/PET 1.9 x 104‘:le Contact-first/PE 1.6 x 10_26 Contact-first/TEFLON 3.0 x 10_2e Proof-first/TEFLON 2-5 x 1° 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 142 Table 33. thass mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film. Treatment Mean PE/Bread 4.8 x 10"la PE/Hi-protein 4.0 x 10'1“” PET/Hi-protien 3.5 x 10’11” PET/Bread 3.0 x 10"1”c PET/Pastry 2,5 x -1bc PE/Pastry 2.0 x 10'1“1 TEFLON/Hi-protein 1.7 x 10'led TEFLON/Bread 1.1 x 10'1“ TEFLON/Pastry 5.1 x 10'39 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 34. thass mean values of Hi-protein, bread, and pastry flour with proof-first, contact-first and no-yeast dough on PE, PET, and TEFLON film. Treatment Mean Bread / None [PE 1 . 1 x 103;, Hiprotein/None/PE 5 . 0 x 10_1bc Bread / None / PET 4 . 7 x 10_1bc Hiprotein /None / PET 4 . 6 x 0_1bcd Hiprotein / None / TEFLON 4 . 1 x 10_1bcde Hiprotein/Proof/PET 3 . 7 x Gammaf Pastry/None/PE 3 . 4 x lo—lcdef Hiprotein/Proof/PE 3 . 2 x o-lcdefg Pastry/Proof / PET 3 . 1 x -1cdefg Pastry/ None / PET 3 . 0 x -lcdefgh Bread / None /TEFLON 2 . 8 x 0_1defgh Hiprotein [Contact / PE 2 . 5 x O-1defgh Bread / Proof /PET 2 . 4 x —1efghi Hiprotein /Contact / PET 2 . 2 x 0_ 18 fghi j Pastry/Proof/PE 2 . 0 X _1efgh1j Bread [Contact [PET 2 . 0 x _1 £9111 jk Bread /Contact/PE 1 . 8 x -1ghijk1 Pastry/Contact/PT 1 . 5 x 10—1hijk1 Bread/Proof/PE 1 . 3 x 10-213k1 Hiprotein/ Proof / TEFLON :2 1): 13-2”,“ Hiprotein/Contact/TEFLON 143 Table 34: (cont'd) Treatment Meanl Pastry/Contact/PE 4.6 x 10'25-5kl Bread/Contact/TEFLON 3.1 x 10'211‘1 Pastry/Proof/TEFLON 1.1 x 10"”1 Bread/Proof/TEFLON 4.0 x 10"31 Pastry/Contact/TEFLON 3.1 x 10"31 Pastry/None/TEFLON 1.3 x 10'31 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test __J'j_-._ Table 35. thass mean values of room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film. Treatment Mean1 PEI/Refri 3.8 x 10:1a PE/Room 3.2 x 10_1a PET/Refri 3.1 x 10_1: PET/Room 3.0 x 10_1b TEFLON/Refri 1.1 x 10_2b TEFLON/Room 8.3 x 10 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 144 Table 36. Wtforce mean values of proof-first, contact- first, and no-yeast dough. Yeast Type Mean1 None 39.80a Proof-first 37.19a Contact-first 15.61” 1 ........................................................ means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test Table 37. Wtforce mean values of Hi-protein, bread, and pastry flour. Flour Type Mean1 Hi-protein 46.47; Bread 30 0 05¢ Pastry 16 o 09 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 145 Table 38. Wtforce mean values of none, proof-first, contact-first, and no-yeast dough with Hi- protein, bread, and pastry flour None/Hiprotein None/Bread Proof/Hiprotein Proof/Bread Contact/Hiprotein None/Pastry Proof/Pastry Contact/Bread Contact/Pastry 1 means followed by the same letters are different at p < 0.05 by Tukey's HSD Test not significantly Table 39. Wtforce mean values of room (23°C) and refrigerated (4°C) temperature with proof-fir and no-yeast dough. Treatment None/Room None/Refri Proof-first/Room Proof-first/Refri Contact-first/Refri Contact-first/Room 1 means followed by the same letter are different at p < 0.05 by Tukey's HSD Test st, contact-first, 46.83a 46.10a 30.26b 29.83b 17.86c 14.32c not significantly . if “ll—guru— ' '2‘ 146 Table 40. Wtforce mean values of room (23°C) and refrigerated (4°C) temperature with Hi-protein, bread, and pastry flour. Treatment Mean1 Hiprotein/Refri 41.10a Hiprotein/Room 38.51a Bread/Room 37.41a Bread/Refri 36.96a Pastry/Refri 15.73” Pastry/Room 15.49” 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test Table 41. Wtforce mean values of proof-first, contact- first, and no—yeast dough with Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature. Treatment Mean Hiprotein/None/Refri 61.32: Bread/None/Room 60.67a Hiprotein/None/Room 58.35a Bread/None/erri 56.54b Hiprotein/Proof/Refri 37.07b Hiprotein/Proof/Room 35.48b Bread/Proof/Room 35.40 c Bread/Proof/Refri 33.34cd Hiprotein/Contact/Refri 24.91d Hiprotein/Contact/Room 21.70 Pastry/None/Room 21-47 Bread/Contact/Refri 21.01 Pastry/None/Refri 20-44 Pastry/Proof/Room 19-90 Pastry/Proof/Refri 19.09de Bread/Contact/Room 16.16ef Pastry/Contact/Refri 7.67f Pastry/Contact/Room 5-10 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 147 Table 42. Wtforce mean values of PE, PET, and TEFLON film. Film Type Mean1 PE 34.80a PET 34.54a TEFLON 23.26 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test Table 43. Wtforce mean values of proof-first, contact- first and no-yeast dough on PE, PET, and TEFLON film. Treatment Mean1 None/PE 51.71: None/PET 49.97b None/TEFLON 37.72b Proof-first/PE 34.93b Proof-first/PET 34.76c Proof-first/TEFLON 20.45c Contact-first/PET 18.89c Contact-first/PE 17.77c Contact-first/TEFLON 11.61 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 148 Table 44. Wtforce mean values of Hi-protein, bread, and pastry flour on PE, PET, and TEFLON film. Treatment Mean PE/Hi-protein 42.62a PE/Bread 42.28a PET/Hi-protein 42.07a PET/Bread 41.42a TEFLON/Hi-protein 34.731” TEFLON/Bread 27.85bc ! PET/Pastry 20.12c , PE/Pastry 19.51c 3 TEFLON/Pastry 7.21 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 45. Wtforce mean values of Hi-protein, bread, and pastry flour with proof-first, contact-f1rst and no-yeast dough on PE, PET, and TEFLON film. Treatment Mean Bread/None/PE 65.85: Hiprotein/None/PE 63.33a Hiprotein/None/PET 60.74ab Bread/None/PET 60.02ab Hiprotein/None/TEFLON 55.44bc Bread/None/TEFLON 49.95c Bread/Proof/PET 42.23c Bread/Proof/PE 40.79c Hiprotein/Proof/PET 39.53cd Hiprotein/Proof/PE 39.35de Hiprotein/Proof/TEFLON 29.95def Pastry/None/PET 29.14ef Pastry/None/PE 25.95ef Hiprotein/Contact/PET 25.94ef Hiprotein/Contact/PE 25.18ef Pastry / Proof / PE 24 . 659:9 Pastry / Proof / PET 3‘2! - 33‘3th Bread/Contact/PET 149 Table 45 : (cont'd) Treatment Mean1 Bread / Contact / PE 2 0 . 2 2‘afgh Bread / Proof [TEFLON 2 0 . 09‘?fgh Hiprote in / Contact / TEFLON 18 . 79fghi Bread/Contact/TEFLON 13.529’}ij Pastry/Proof/TEFLON 11 . 33tujk Pastry/Contact/PET 8.71ijk Pastry/Contact/PE 7.92jk Pastry/None/TEFLON 7.77jk Pastry/Contact/TEFLON 2.53k 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 46. Wtforce mean values of room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON f1lm. Treatment Mean1 PE/Refri 35.32: PET/Refri 34.84a PE/Room 34.29a PET/Room 34.23b TEFLON/Refri 23.64 TEFLON/Room 22-89 1 means followed by the same letter are not significantly different at p < 0.05 by Tukey's HSD Test 150 Table 47. thass mean values of proof-first, contact- first, and no-yeast dough at room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film. Treatment Mean None/Refri/PE 6.8 x 10’1'a None/Room/PE 6.4 x 10'1'Ii None/Refri/PET 4.3 x 10'3” None/Room/PET 4.0 x 'd”° Proof/Room/PET 3.2 x '1”°d Proof/Refri/PET 3.0 x '1”°d None/Refri/TEFLON 2.5 x 1 '1Cde Contact/Refri/PE 2.3 x 10'lde Proof/Refri/PE 2.2 x 1"me Proof/Room/PE 2.2 x 10'139 None/Room/TEFLON 2.1 x 1 :1: Contact/Refri/PET 2.0 x -ddef Contact/Room/PET 1.7 x 10_2 : Contact/Room/PE 9.4 x 104: Contact/Refri/TEFLON 3.7 x 10_2f Proof/Refri/TEFLON 2.9 x 10__2f Contact/Room/TEFLON 2.2 x 10-2: Proof/Room/TEFLON 2.0 x 10 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test Table 48. Wtforce mean values of proof-first, contact- first, and no-yeast dough at room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film. None/Room/PE None/Refri/PE None/Refri/PET None/Room/PET None/Refri/TEFLON None/Room/TEFLON Proof/Room/PET Proom/Room/PE Proof/Refri/PE Proof/Refri/PET Contact/Refri/PE Proof/Room/TEFLON Proof/Refri/TEFLON Contact/Refri/PET Contact/Room/PET Contact/Room/PE Contact/Refri/TEFLON Contact/Room/TEFLON 34 . 93d°f9 34 . 93‘”afg 34 . 39"“9 20 . 85““9 20 . 73"“9 20. 18‘mfg 20. 06‘1919 17 . 72‘“? 14 . 69°19 12.67f9 10.559 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 152 Table 49. thass mean values of Iii-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film. Treatment Mean Bread/Refri/PE 5.3 x 10'1“ Brfiaci/Rlll/Pli! 4.4 x 10'1"10 Hiprotein/Refri/PE 4.0 x -1abc Hiprotein/Refri/PET 3.5 x '1”°d Hiprotein/Rm/PET 3.4 x 10'1”“ Hiprotein/Rm/PE 3.2 x 0'1”“: Bread/Refri/PET 3.2 x 0'1gcgef Bread/Rm/PET 2.9 x 0': :1 : Pastry/Rm/PET 2.5 x 0:12:th Pastry/Refri/PET 2.5 x 0_1: : : Pastry/Refri/PE 2.0 x 10__m°f<3h PastrY/Rm/PE 1.9 x 104;: Hiprotein/Refri/TEFLON 1.9 x 10__1f :1 Hiprotein/Rm/TEFLON 1.6 x 10%:i Bread/Refri/TEFLON 1.2 x 104:1 Bread/Rm/TEFLON 9.0 x 10_31 Pastry/Refri/TEFLON 8.0 x 10_31 Pastry/Rm/TEFLON 2.3 x 10 1 means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test 153 Table 50. Wtforce mean values of Hi-protein, bread, and pastry flour at room (23°C) and refrigerated (4°C) temperature with PE, PET, and TEFLON film. Treatment Mean1 Hiprotein/Refri/PE 44.05” Hiprotein/Refri/PET 43.26”” Bread/Refri/PE 42.43”” Bread/Room/PE 42.14”” Bread/Room/PET 41.89”” Hiprotein/Room/PE 41.18”” Bread/Refri/PET 40.95”” Hiprotein/Room/PET 40.88”” Hiprotein/Refri/TEFLON 35.99””c Hiprotein/Room/TEFLON 33.47”c Bread/Room/TEFLON 28.19Cd Bread/Refri/TEFLON 27.52”” Pastry/Refri/PET 20.31” Pastry/Room/PET 19.93d Pastry/Room/PE 19.53” Pastry/Refri/PE 19.48” Pastry/Refri/TEFLON 7.40e Pastry/Room/TEFLON 7.01e means followed by the same letters are not significantly different at p < 0.05 by Tukey's HSD Test BIBLIOGRAPHY “m "l BIBLIOGRAPHY Adam, N. R., (1968). The physics and chemistry of surfaces. Dover : New York, NY. Alfrey, T. Jr., (1948). Mechanical Behavior of High Polymers, Wiley-Interscience : New York, NY. Allan, A. J. G. (1959). The spreading of liquid on polyethylene film; The effect of preprinting treatments. Journal of Polymer Science, 38, 297. Allen, R. W., (1978). Theories of Adhesion. In Booth, K (Ed.). (1990). 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