School of Material Science and Engineering

The University of New South Wales

Physical Performance Properties and Morphological Characteristics of Dibenzylidene Sorbitol-solidified Propylene Glycol-Glycerin Matrices containing Mild Surfactants for Personal Cleansing

A Thesis

Danilo L. Lambino

Submitted in the Fulfillment of the Requirements of the Degree of Master of Science (MSc) August 2002 11

CERTIFICATE OF ORIGINALITY

I hereby declare that this submission is my own work and that to the best of my knowledge and belief, it contains no material previously published or written by another person, nor material which to a substantial extent has been accepted for the award of any degree or diploma at UNSW or any other institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis.

I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged. Ill

ACKNOWLEDGEMENTS

I gratefully acknowledge Johnson & Johnson for funding this research and the many people who contributed to this study. I would especially like to thank:

Dr. Sri Bandyopadhyay, my graduate supervisor for his guidance, support and encouragement.

Dr. Aibing Yu, my graduate co-supervisor for his support and technical advice.

Mr. Noble Mathew, my industry supervisor, for his commitment and passion for this research study.

Mr. Gary Gao of UNSW and Dr. Susan Niemiec of Johnson & Johnson Topical Formulations and Drug Delivery Research Center for her technical support on the Freeze Fracture Transmission Electron Microscopy.

Ms. Bettina Wolpensinger, Ms. Katie Levick, and Ms. Margaret Budanovic of the UNSW Electron Microscopy Unit for their technical assistance.

Finally, and most important, rry mother Ligaya and sisters Lala and Lyn for being an enduring source of strength, inspiration and unfailing support. IV

ABSTRACT

Dibenzylidene sorbitol (DBS), a low molar mass butterfly-shaped amphiphile, is an effective solid gelator for organic liquids and polymeric melts. It can strongly interact through hydrogen bonding and self-associate into a three-dimensional nanofibrillar network. DBS finds practical applications in commercially important polyolefins such as polyethylene, which are primary components for packaging and construction materials. It acts as a nucleating agent in the formation of spherulites improving the polymer's optical clarity, yield and tensile strength. In personal care products, DBS is used as a solidifying agent for transparent antiperspirant and deodorant sticks.

In this study, we have investigated the use of DBS in solidifying mild surfactant systems mixed with polar organic solvents glycerin and propylene glycol. These solid matrices can be used as milder cleansing alternatives to bar soaps, which are harsh on skin.

The physical performance properties of the DBS-solidified matrices were defined through predictive model equations and then optimized using the principles and techniques of Mixture Design Experiments (MOE). The resultant optimised matrices have better bar wear rate and bar mush with comparable transparency to commercially available transparent soaps like Johnson's Baby Clear Soap. Also, given the V

technology limitations the cleansing bar matrix was shown to have acceptable hardness and level of foaming. However, the major drawback is the matrix' susceptibility to syneresis when exposed to high humidity due to the presence of high concentrations of propylene glycol and glycerin in the formula. It was found 1hat addition of free water reduces syneresis but also reduces rigidity and clarity of the matrix.

This study also investigated the morphology of DBS in the matrix via Atomic Force

Microscopy and Freeze Fracture Transmission Microscopy. Topographic images

show distinct formation of long nanofibrils and fibrillar bundles of DBS with each

fiber cross-section measuring about 40nm. The twisting, interconnection and multidirectional percolation network of DBS fibers provided rigidity to the matrix.

Introducing free water into the system results to a remarkable change in DBS morphology with thinner fiber cross-sections and absence of crosslinking, consistent with the loss of structure of the matrix. VI

TABLE OF CONTENTS SECTION PAGE

Certificate of Originality 11 Acknowledgement lll Abstract IV Table of Contents VI List of Figures Xl List of Tables XVI List of Equations XVlll List of Appendices XIX

I INTRODUCTION

II LITERATURE REVIEW 5

2.1 Dibenzylidene Sorbitol 5 2.1.1 Chemistry, synthesis and manufacture 5 2.1.2 Physico-chemical properties 9 2.1.3 Solubility 10 2.1.4 Morphological behaviour in various systems - DBS and its derivatives 13 2.1.5 DBS application in personal care formulations 24

2.2 Non-dibenzylidene sorbitol solid gel formers 27 2.2.1 Soap 27 2.2.2 Gelatin 30 2.2.3 Fatty alcohols and waxes 32

2.3 Advantages of DBS 35 2.3.1 Stability and compatibility 35 VII

SECTION PAGE

2.3.2 Safety and toxicology 35 2.3.3 Transparency of solidified matrix 35

2.4 Disadvantages of DBS 37 2.4.1 Insolubility in water 37 2.4.2 High temperature dissolution 37

2.5 Commercially available cleansing bar matrices 38 2.5.1 Opaque sodium soap bar 38 2.5.2 Translucent or pearlized soap bar 41

2.5.3 Transparent soap bar 41 2.5.4 Syndet bar 42

III SCOPE OF PRESENT WORK 48

IV MATERIALS, METHODS AND DESIGN 49

4.1 Raw Materials 4.1.1 Polar Solvents 49

4.1.2 Surfactants 52 4.1.2.1 Anionic surfactants 52 4.1.2.2 Nonionic surfactants 54 VIII

SECTION PAGE

4.1.2.3 Amphoteric surfactants 54 4.1.3 Gelling synergist 56

4.1.4 Chelating agent 57

4.2 Test Methods for Physical Performance Properties 58

4.2.1 Bar penetration 58

4.2.2 Bar mush 61

4.2.3 Foam volume tumbling tube 63 4 .2.4 Bar wear 65

4.2.5 Syneresis 67 4.2.6 Transparency 69

4.3 Test Methods for Morphological Characterization 72

4.3.1 Atomic force microscopy 72

4.3.2 Freeze fracture transmission electron microscopy 76

4.4 Experimental Procedure 78

4. 4 .1 Objectives of the experiment 79 4.4.2 Identification of critical cleansing bar properties 80 4.4.3 Identification of ingredient range cf concentrations 82

4.4.4 Selection of mixture design 85

4.4.5 Experimentation and preparation of product formulations 87 IX

SECTION PAGE

V RESULTS AND DISCUSSION 91

5.1 Mixture Design Analysis 91

5.1.1 Model Equation Selection 94 5.1.1.1 Model Fit 94

5.1.1.2 Analysis of Variance 97 5.1.1.3 Diagnostics - Bar wear example 98 5.1.1.3.1 Normal Plot 99 5.1.1.3.2 Residual versus predictive plot 99

5.1.1.3.3 Residual versus run 100 5 .1.1. 3 .4 Residual versus factor 101 5.1.1.3.5 Outliers 101 5.1.1.3.6 Cooks distance 102

5 .1.1. 3. 7 Leverage 102 5.1.1.3.8 Predicted versus actual plot 103 5.1.1.3.9 Box-Cox plot 103

5.2 Predictive Model Equations and Graphs 104

5.2.1 Bar hardness 107

5 .2.2 Bar mush 108 5.2.3 Bar wear 109 5.2.4 Foam volume 110 X

SECTION PAGE

5.2.5 Transparency 112 5.2.6 Syneresis 113 5.2.6.1 Effect of equilibrium moisture concentration 114 5.2.6.2 Effect of hydroxypropyl cellulose in competitive hydroge1r 125 bonding 5 .2.6.3 Effect of higher DBS concentration 126

5.3 Mixture Optimization 129

5.4 Morphological Characterization 137

5.4.1 Surface topography analysis 138 5.4.2 Effect of HPC on the morphology of DBS in the matrix 144 5.4.3 Effect of free moisture on the morphology of DBS in the matrix 147 5.4.4 Morphology of soap bar matrices 150 5.4.5 Freeze fracture transmission microscopy 152 5.4.5.1 DBS and HPC in surfactant matrices 153 5.4.5.2Clear and opaque soap structures 157

VI CONCLUSION 160

VII RECOMMENDATIONS FOR FURTHER WORK 162

VIII LIST OF REFERENCES 164 Xl

LIST OF FIGURES

Figure Title Page

Antiperspirant and deodorant stick products 3

2 DBS molecule 5

3 DBS synthesis 6

4 Process flowchart for Disorbene LC manufacture 8

5 Polarized light microscopy image of DBS particles 9

6 Dissolution profile of DBS in various solvents 11

7 SEM micrographs of DBS network in PDMS 14

8a Scanning electron micrographs of DBS network at 15 high magnification

8b Scanning electron micrographs of DBS network at low 16 magnification

9 Polarized light micrographs of DBS network revealing 17 a highly ordered structure of birefringent spherulites

10 Dynamic viscoelastic moduli shown as a function of 18 strain (Y) for a 1% DBS gel

11 Electron Micrographs of D-DBS in solvents with 19 different donor number

12 Morphological investigation via TEM of crystalline DBS 21 with PPO and PP

13 TEM images of DBS in PPO12 gel matrix at two 22 different magnification XII

Figure Title Page

14 Soap processing routes 28

15a Gelatin's amino acid composition 30

15b Gelatin's structural chain 31

16 Transparency of gelled solvent versus DBS concentration 36

17 Soap processing and finishing process 39

18 Soap finishing line (Mazzoni LB) 40

19 Chemical structure of glycerin and propylene glycol 51

20 General chemical structure of anionic surfactants 53

21 Chemical structure of anionic surfactants used 53

22 Class chemical structure of sorbitan ester 54

23 Chemical structure of amphoteric surfactants used 55

24 Idealized structure of HPC, molar substitution= 3.0 56

25 Disodium EDTA chemical structure 57

26 Penetrometer equipment-product set-up 59

27 Soap mush test procedure 62

28 Foam volume tumbling tube equipment 65

29 Humidity chamber 68

30 Basic AFM set-up 73

31a AFM Equipment set-up 73

31b Basic scanning probe microscopy components 74 Xlll

Figure Title Page

32 Summary of Mixture design experiment program 78

33 Processing steps in making cleansing bar matrix 87

34 Fit summary for bar wear 95

35 Model term selection 96

36 ANOVA for complete quadratic term 97

37 ANOV A with insignificant term removed 98

38 Normal plots of residuals 99

39 Residual versus predicted 100

40 Residual versus run 100

41 Residual versus DBS 101

42 Outlier 101

43 Cook's distance 102

44 Leverage versus run 102

45 Predicted versus actual plot 103

46 Box-Cox plot for power transmission 103

47 Model graph and equation 106

48 Trace (Piepel) plot 107

49 Trace Plot for bar wear at different ingredient 110 combinations

50 Foam volume versus bar wear profile 111

51 Foam volume trace plot 111 XIV

Figure Title Page

52 Transparency trace plot 112

53 Images of bars exposed to 60% relative humidity 115 and 2s'C for 48 hours

54 Comparative moisture adsorption profile 121

55 Trasnsmittance versus free water content 123

56 Penetration versus free water content 124

57 Moisture adsorption profile at different HPC 127 concentrations at 60% RH, 40° C

58 Moisture adsorption profile 1.0% versus 3.0 DBS 128

59 Numerical optimization criteria sheet 132

60 Optimal solution overlay plot 136

61 Three dimensional topographic AFM image of Sample 1 142

62 AFM Section analysis of Sample 1. 143

63 Three dimensional topographic AFM image of Sample 2 145

64 AFM Section analysis of Sample 2. 146

65 AFM Section analysis of Sample 3. 148

66 Three dimensional topographic AFM image of Sample 4 149

67a 5µm x $1-m AFM image of clear soap 150

67b 5µm x $1-m AFM image of opaque soap 151

68 Freeze fracture TEM image of DBS + HPC solid gel 154 matrix xv

Figure Title Page

69 Freeze-fracture TEM image of DBS only solid gel 155 matrix

70 Freeze-fracture TEM image of HPC only gel matrix 156

71 Freeze-fracture TEM image of JB Clear Soap solid 158 matrix

72 Freeze-fracture TEM image of Opaque soap solid 159 matrix XVI

LIST OF TABLES

Table Title Pae;e

1 Composition of the $ 1.4 Billion US deodorant and 2 antiperspirant market, 1992

2 Top Five deodorant brand shares in Western Europe 3

3 Common polar solvents for DBS 10

4 Clear antiperspirant stick composition 25

5 Sodium-stearate based stick 29

6 Antiperspirant dry stick 32

7 Lotion stick (Abitec) 33

8 Lip balm composition (Aarhus Oliefabrik A/S) 34

9 Lipstick (Mobil Chemicals) 34

10 Typical baby soap composition 38

11 Patented syndet bar composition 43

12 Opaque soap bars 44

13 Translucent soap bars 45

14 Transparent soap 46

15 Syndet bars 47

16 Typical physico-chemical properties of propylene 51 Glycol and glycerin

17 Bar properties, benchmark, criteria and optimization 81 Goal

18 Variable and fixed components 84

19 Experimental design data 86

20 Mixture design worksheet 93 XVII

Table Title Page

21 Correlation analysis of component versus 108 response variable

22 DBS-solidified bar matrix formula sheet 117

23 % free moisture of samples for syneresis test 118

24 Optimization criteria 131

25 Optimal solutions 133

26 Predicted versus actual response data 134

27 Formulations subjected to AFM 140

28 Internal structure comparison 152 XVlll

LIST OF EQUATIONS

Equation Description Page

4.2.2 Percent mush 63

4.2.3 Foam height 65

4.2.4 Percent bar wear 67

4.2.5 Syneresis in g/m2 69

4.2.6a Percent transmittance 70

4.2.6b Mean degree of transparency 71

5.2. l Model equation for penetration 104

5.2.2 Model equation for bar mush 104

5.2.3 Model equation for bar wear 104

5.2.4 Model equation for foam volume 105

5.2.5 Model equation for transparency 105

5.2.6 Model equation for syneresis 105

5.2.6.1 Equilibrium moisture concentration 119

5.3 Desirability index 129 XIX

LIST OF APPENDICES

Appendix Title

Material Specifications - Propylene Glycol

2 Material Specifications - Glycerin

3 Material Specifications - Sodium Laureth Sulfate

4 Material Specifications - Sodium Lauretlr 13 Carboxylate

5 Material Specifications - POE Sorbitan Laurate

6 Material Specifications - Cocamidopropyl Betaine

7 Material Specification - Sodium Lauroamphoacetate

8 Material Specification - Hydroxypropyl Cellulose

9 Material Specification - Disodium EDTA

10 Material Specifications - Dibenzylidene Sorbitol

11 Statistical Analysis for Bar Mush, Penetration, Foam, Syneresis and Transparency

12 Rheology modifiers and their solubility in Propylene glycol Chapter I. Introduction

I INTRODUCTION

Dibenzylidene alditols (sorbitol, xylitol, ribitol) are important components in industrial and personal care compositions for a variety of applications. Recent studies demonstrate how Dibenzylidene Sorbitol (DBS), the most commercially viable of the alditols, acts as a nucleating agent in the formation of spherulites in commercially important poly olefin such as polyethylene 1. The resultant polyethylene showed improved optical clarity, yield and tensile strength for practical applications in packaging and construction materials. In personal care,

DBS is used mainly as a solidifying agent for anti-perspirant and deodorant sticks formulations.

DBS is a low-molar-mass organic molecule that is capable of physically gelling organic liquids and polymeric melts. DBS molecule can strongly interact through hydrogen bonding and self-associate into a three-dimensional nanofibrillar network in a suitable organic solvent. The morphological characteristics of DBS depend strongly on solvent polarity, as expressed in the proton donor number of the solvent. 2 Chapter I. Introduction 2

DBS has played a significant role in the development of clear solid deodorant and antiperspirant stick compositions,3~ which prior to the use of DBS relied mainly on sodium soap to form a solid structure. The perceived need for a clear solid stick has evolved since transparency to the consumer implies mildness, purity and more elegance and to the marketer it offers another route of entry to a new market capitalizing on these consumer perceptions 7. A significant portion of the US

Antiperspirant and Deodorant market in 1992 is based on stick formulation at

52% market share worth $ 730 million (Table I). 6 In 2000 the size of the US market has reached $1. 949 Billion. 8

Table 1. Composition of the $ 1.4 Billion US deodorant and antiperspirant market, 1992 6

ANTIPERSPIRANT DEODORANT

Sticks Roll-ons Aerosol Pump/others Sticks Aerosol

38% 22% 18% 4% 14% 4%

Some of the commercially available deodorant and antiperspirant products are shown in Figure 1. Chapter I /11/roduclion 3

ClV L G ,'\.RI

.. ___ _ _..____.. .. _ J...,,, I

Figure 1. Antiperspirant and deodorant stick products

The top 5 deodorant brand shares in Western Europe are shown in Table 2.

Table 2. Top five deodorant brand shares in Western Euro pe

Brand Company %, Retail Value Axe/Lynx/Ego Unilever 10.2 Nivea Beiersdorf 7.3 Rexona Unilever 5.6 Dove Unilever 4.6 Sure Unilever 4.5 Chapter I. Introduction 4

DBS in an organic solvent-surfactant matrix will find other practical applications in the cosmetic and household industry other than a gellant for antiperspirant and deodorant sticks 3. For example, it can be used in a solid cleansing implement both for personal care and laundry use, a matrix to deliver actives on the skin, a solid hair gel, sunscreen stick, and insect repellent stick. The surfactant in the different matrices can function in many ways: a) provide detergency, b) emulsifier for active ingredients and fragrances, c) clarifying agent and d) encapsulating material for hydrolytically sensitive ingredients.3

Cleansing products in bar form is still the consumers' preferred form of cleansing worldwide because it is economical, easy to use and by consumer usage habit.

By gelling surfactants systems with DBS to form solid cleansing bars, consumers will find a milder alternative to traditional sodium soap bars, which are harsh on skin.

This study focuses on defining the physical performance properties and morphological characteristics of DBS as used in !J!lling mild surfactants to deliver a solid cleansing bar for use on infants and children and those adults with sensitive skin. Chapter II. Dibenzylidene Sorbitol - Chemistry, Synthesis and Manufacture s

II LITERATURE REVIEW

2.1 Dibenzylidene Sorbitol

2.1.1 Chemistry, Synthesis and Manufacture

Dibenzylidene Sorbitol (DBS) is the most commercially important of the dibenzylidene alditols. It is a low-molar-mass organic molecule capable of physically gelling organic liquids and polymeric melts. The chemical structure of this butterfly shaped amphiphile is shown below':

0 0-HC /'CHH-6~0 ""o-f-H)CH-0 H-C-0 I H-C-OH I /CH2 HO

Figure 2. DBS molecule 9 Chapter II. Dibenzylidene Sorbitol - Chemistry, Synthesis and Manufacture 6

DBS 1s synthesized via dehydro-condensation reaction of 2 moles of benzaldehyde with 1 mole of sorbitol in an aqueous solution in the presence of a mineral acid catalyst1°: HO...... _ r2 H-1-oH H0-1-H H-1-0H H-1-oH /CH2 HO

Figure 3. DBS synthesis 10

DBS molecule can strongly interact through hydrogen bonding and self-associate into a three-dimensional nanofibrillar network in a suitable organic solvent and temperature condition. The morphological characteristics of DBS depend strongly on solvent polarity, as expressed in the proton donor number of the solvent.11

Several variations of the above process were developed for greater efficiency, high purity and yield. An example of the process is described in US Patent

4,267,110 by Uchiyama where DBS is produced in 2 stages10. The first stage involves reacting at 5

benzaldehyde in the presence of 0.03 to 0.5 parts by weight of hydrochloric acid.

The first stage reaction is shifted to the second stage when the concentration of

DBS formed reaches 10-40%. The second stage involves addition of water at concentration of at least 2.5 times and catalyst at 0.02 to 0.5 times the weight of sorbitol charged in the first stage. The second stage reaction occurs in a suspended state at temperature of 15°C to 25°C with DBS obtained as an aqueous suspension.

Roquette Freres has developed and patented a new process,4 which is via heterogeneous phase acid catalysis, allowing synthesis of high purity dibenzylidene sorbitol. Details of the process are presented in Figure 4. Chapter II. Dibenzylidene Sorbitol - Chemistry, Synthesis and Manufacture 8

Sorbitol + Benzaldehyde

Acetalyzing

Filtration

....- Water

Washing

Drying

Packaging

Disorbene™ LC

Figure 4. Process flow chart -Disorbene LC manufacture (Roquette Freresf Chapter [I. Dihenzy lidene Sorhilol - Soluhilily 9

2.1.2 Physico-chemical Properties

DBS is a finely ground white rod-like granular powder with the following physico-chemical properties as defined in one of its commercially available product, Disorbene LC from Roquette Chemicals12:

Melting Point : 224°-22g:>c Bulk Density: 0.25 Kg/l Moisture Content: 1.5 +/ - 0.2% Assay: 98% Mininum Shape: Rod like

IOµm

Figure 5. Polarized light microscopy image of DBS particles Chapter II. Dibenzylidene Sorbitol - Solubility lO

2.1.3 Solubility

The presence of 2 benzaldehyde structures along the sorbitol backbone makes

DBS insoluble in water. 4 However, DBS can gel most polar organic solvents in which it is soluble. This includes alcohols, glycols, PEGs, amines, amides, ethers and esters. Non-exhaustive list is shown in Table 3.

Table 3. Common polar solvents for DBS

Chemical Empirical Formula

Ethanol C2H60

Isopropanol C3HsO

Ethylene Glycol C2H602

Diethylene Glycol C4H1003

Triethylene Glycol C6H1404

PEG 200 C6H1404

Propylene Glycol CJHs02

Dipropylene Glycol C6H1403

Butylene Glycol C4H1002

Octy ldodecanol C20~20

Glycerine C3Hs03 Chapter II. Dibenzylidene Sorbitol - Solubility 11

Figure 6 shows dissolution curves of DBS in various pure solvents. The curves show an asymptotic tendency. From a certain incorporation level, dissolving a larger quantity of DBS requires a small amount of additional energy. The above dissolution profiles were studied up to 5% DBS content, the maximum level it can incorporated in a solid stickcomposition. 4

)0 20 .______. ______..._ ____ ...__ ___......

0 2 ) 4 s PERCENTAGE OF DISORBE.'°'E ...... _ ETKA."OL -- PEO 200 ...... PEG-WO -e- P'ROPYl.E."lE GLYCOL ...._. 01PROPYl.E.."'E GL YC ...._ BUT'ft.ENE GLYCOL

Figure 6. Dissolution profile of DBS in various solvents 5

DBS is likewise soluble in polar oils like Isopropyl myristate, G2-C1s alcohol benzoate, Polypropylene Glycol (or PPG) -27 Glycerylether, PPG-5 Ceteareth 20 Chapter II. Dibenzylidene Sorbitol - Solubility 12

and PPG-3 Myristyl Ether. However, the dissolution is limited with the very high temperature and the amount of polar solvents required to dissolve DBS. 4 Chapter II. Dibenzylidene Sorbitol -Morphology and Rheological Behaviour 13

2.1.4 Morphology and Rheological Behavior in Various Systems - DBS and its Derivatives

DBS, through hydrogen bonding, self-organizes at relatively low concentrations to form a three-dimensional percolation network in low molecular weight organic liquids 13. The resultant network induces physical solid gellation, which can be mechanically and thermally reversed. If mixed with a semi-crystalline homopolymer (e.g. isotactic polypropylene 14 or polyethylene terphthalate15) in the molten state, DBS acts as a nucleating agent; reducing crystal size upon solidification and subsequently enhancing optical transparency. In amorphous homopolymer however, such as polystyrene and polycarbonate, DBS phase separate into aggregates measuring 0.1-0.2 µm 16

Spontak and Ilzhoefer17 studied the effect of aidition of polymer graft on the morphology of self-assembled DBS in Polydimethyl siloxane (PDMS). DBS in pure PDMS assembles into loosely connected fibrils and fibrillar bundles 70 nm thick and tens of micrometers long. Incorporation of polyoxyethylene grafts along the PDMS backbone yields layered sheets of DBS, whereas grafted poly

(oxypropylene) produces a percolation network with connective fibrils measuring

10-20 nm in diameter. Such morphological variations reflect molecular interactions between DBS and the dissimilar monomer sequences in each Chapter II. Dibenzylidene Sorbilol -Morphology and Rheological Behaviour 14

polymer. Figure 7 shows SEM Micrographs illustrating the morphological characteristics of DBS formed in PDMS homopolymer at different magnification.

The low magnification images in Figures 7a and 7b reveal that DBS self assembles into long fibrils and fibrillar bundles. Note that many of the fibrils in

Figures 7c and 7d appear faceted.

Figure 7. SEM micrographs of DBS network in PDMS17 Chapter II Dibenzylidene Sorbilol -Morphology and Rheolog,cal Behaviour IS

Addition of a small quantity (<2 wt%) of DBS to a homogeneous, disordered amphiphilic graft terpolymer yields a gel network with two levels of structural organization. 18 From scanning electron micrographs shown in Figure 8 a) and b), a fine percolation network comprised of fibrillar strands measuring 10. 20nm results from the interactions between the gellant and terpolymer. 18

10 µm

Figure Sa. Scanning electron micrographs of DBS network at high magnification18 Chapter rI Dibenzylidene Sorbitol -Morphology and Rheological Behaviour 16

100 µm

Figure 8b. Scanning electron micrographs of DBS network at low magnification 18

Figure 9 shows a polarized light microscopy image of the DBS containing graft tertpoylmer revealing a highly ordered structure consisting of strongly birefringent spherulites. [t also shows that each spherulite emanates radially from a nucleation site. 18 Chapter II. Dibenzy fidene Sorbitol - Mo,phology and Rheological Behaviour 17

!Oum

Figure 9. Polarized light micrograph of DBS network revealing a highly ordered structure consisting of birefringent spherules 18

Dynamic rheological measurements (Figure l 0) reveal that these two distinct levels of microstructural organization attributed to the presence of DBS in the graft tertpolymer are responsible for a) deformation mechanisms exhibited at different strain levels and b) ability to recover upon mechanical and thermal recycling. 18 Sample of a I% DBS in PDMS graft terpolymer was deformed sinusoidally at varying strain amplitudes (y) and frequency, and the corresponding elastic (G') and loss (G") moduli were measured at ambient temperature. At low strain, the moduli are relatively insensitive to y indicative of a linear viscoelastic regime, and G" is significantly lower than G'. As y increases, the gel microstructure is disrupted, in which case G ' decreases, eventually becoming Chapter II. Dibenzylidene Sorbitol -Morphology and Rheological Behaviour 18

smaller than G". At about 3.2% strain, the G'-ycurve crosses the G"-ycurve.

This crossover is characteristic of physical gels 19• 20 and corresponds to strain induced transformation of the gel from solid-like to liquid-like behaviour.

107

N -E 10•

~>,, "'C 105 -'S "'C 0 10' Solid- ~ like

103 10-1 10° 101 ,02 103 y (%) Figure 10. Dynamic viscoelastic moduli shown as afunction of strain (y) for a 1 % DBS gel

Yamasaki et. at_ll investigated the morphological dependence of D-DBS (a chemical derivative of DBS) in the polarity of solvents, measured by the proton donor number (ON). In low polar solvents, the gel held a mesh type network structure in which the fiber appeared to be a rope- like helical structure. In moderately polar solvents, the gel held an isotropic mesophase and in polar solvents, a spherulite-texture was observed. By IR spectroscopic measurements, Chapter II. Dibenzylidene Sorbitol - M01phology and Rheological Behaviour 19

it was observed that, with the increase in solvent polarity, hydrogen bonding between DBS and solvent became more predominant than the intramolecular hydrogen bonding, and the hydrogen bonding between DBS became weaker at the same time. Figure 11 shows Electron Micrographs of o-DBS gel in different solvents of different proton donor number.

a. p-xylene (DN = 27.9) b. 1,4-dioxane (DN = 96) c. dimethyl siloxane (DN = 149.6)

Figure 11. Electron Micrographs of D-DBS in solvents with different donor number1 3

If a molten polymer modified by DBS such as polycarbonate or polystyrene undergoes vitrification as it cools from the molten to ambient temperature, the

DBS molecule phase separate into aggregates measuring 100-200 nm in size based on light scattering technique. 21 [n the presence of crystallizable polymer chains, DBS induces gelation1"· 15 at temperatures above the polymer melting temperature and subsequently promotes heterogeneous crystal nucleation at Chapter II. Dibenzylidene Sorbitol -Morphology and Rheological Behaviour 20

reduced temperature. 22' 24-32 As a nucleating agent, the high surface area of DBS nanofibrils (at - 400 m2/g, assuming nanofibrils 10 nm in diameter2 3 ) assist polymer chains to crystallize into numerous small spherulites, which, in turn, endow the polymer with enchanced mechanical strength and, depending on spherulite size, optical clarity. Thiery et al. 23 have proposed an efficiency scale based on seeded versus unseeded crystallization temperatures for nucleating agents used in conjunction with isotactic polypropylene. According to their scale,

DBS is rated relatively high at 41 % near 4pyridinecarboxylic acid at 39% and lower only to 4biphenyl carboxylic acid, which is rated highest at 66%. 2,3- pyridine dicarboxylic acid was rated the lowest at 13%.

DBS morphology at very small concentration, i.e. below 5% in systems such as

Polypropylene Oxide (PPO), Polystyrene (PS) and Polypropylene (PP) was also investigated. This shows that even at concentration below 5%, DBS provide strong reinforcing effects on the polymer matrices. TEM images of solution cast, unstained films show network-like structures of arborescent bundles of crystalline

DBS. 33 The fibrils shown in Figure 13a and Figure 13b have diameters of about

20nm and can reach lengths of microns. Chapter II. Dibenzylidene Sorbilol - Morphology and Rheological Behaviour 21

a. PPO+ 3% DBS 1 um

b. PP + 0.5% DBS

Figure 12. Morphological Investigation via TEM of crystalline DBS with PPO and PP Polymers 33 Chapter II. Dibenzylidene Sorbitol -Morphology and Rheological Behavwur 22

c. PS+ 5% DBS l50mn

Figure 12. Morphological Investigation via TEM of crystalline DBS in PS33

DBS morphology was also studied in amorphous polypropylene oxide matrices.

The effect of very small amount of DBS < 0.3% showed marked improvement on the elasticity and viscosity compared to neat matrix. This improvement is attributed to the formation of DBS network as shown on TEM images in Figure

13 . It reveals a fine, three-dimensional structure of DBS consisting of fibrils measuring approximately I O nm in diameter and some fibrillar bundles. Chapter II. Dihenzy lidene Sorhito/ - M01phology and Rheological Behaviour 23

Figure 13. TEM images of DBS in PP012 gel matrix at two different magnifications Chapter II. DBS Applications in Personal Care Formulations 24

2.1.5 DBS Application in Personal Care Formulations

DBS is known in the personal care industry and is used mainly as primary gellant in clear deodorant and antiperspirant stick formulations. 4,6-s,13 US Patent

5,895,644 (Albanese et. al.) discloses a translucent anti-perspirant composition comprising of a) DBS; b) selective derivatized guar, especially a hydroxy C3-C4 alkyl guar; and c) organic solvent unreactive to DBS in the presence of an acid catalyst. 35

US Patent 5,286,755 (Kauffman et al.) reference to a solid, transparent non alcoholic cosmetic gel containing 65 to 99% of a polyol, 0.1 to 5% of DBS, 0.1 to

5% of a hardening agent of the sulfosuccinate type and 0.5 to 40% water. The gel is employed in a make-up product. 36

US Patent 4,743,444 (McCall) discloses cosmetic stick compositions consisting from about 10% to about 97% of a liquid base material, from about 1% to about

10% of a benzylidene sorbitol, and from about 1% to about 15% of a C14-C16 fatty alcohol. The cosmetic sticks preferably also contain a deodorant or an antiperspirant active.37 Chapter 11. DBS Applications in Personal Care Formulations 25

Roquette Disorbene Le Forrnulaf18 discloses a sunscreen stick composition of

DBS and dissolved in propylene glycol, PEG 300 and propylene carbonate. Zinc

Oxide was used as the inorganic sunscreen active. The first antiperspirant stick composition gelled by DBS that has been reported appear in the US Patent

4,154,816 was disclosed by Roehl and Tar/3 in 1979 and is shown in Table 4. The inventors claimed excellent antiperspirant efficacy, good product stability and tolerance on people with sensitive skin. 13 This transparent solid stick consisted of one or more acidic antiperspirant salts dissolved in a lower monohydric alcohol like ethanol and specific polyhydric alcohols.

Table 4. Clear antiperspirant stick composition13

Ingredient %w/w Dibenzylidene Sorbitol 2.00

Ethyl Alcohol 40.00

1,2 Propylene Glycol 28.70

2,4,4' -Trichloro-2' -hydroxy-diphenyl ether 0.30

Coconut Fatty Acid monoethanolamide 3.00

Fragrance 1.00

Ethylene glycol/propylene glycol-polycondensate 15.00 aluminum hydroxychloride propylene glycol complex 10.00 Chapter II. DBS Applications in Personal Care Formulations 26

In a second patent (US Patent 4,346,079), Roehl improved the physical properties of the clear stick by controlling the level of the propylene-ethylene condensate.39

Later examinations of formulations using Roehl patents found that, although initially stable, these sticks did not have sufficient shelf life to be commercially viable." 0 Chapter II. Non.lJBS Solid Gel Formers -Soap 27

2.2 Non-DBS Solid Gel Formers

2.2.1 Soap

Soap is generally regarded as either the alkali or ammonium salts of fatty acids that delivers the right combination of cleaning, lathering and surfactant properties.41 Its principal use is in the form of a soap bar for personal cleansing.

Cleansing bar is still the consumer's preferred form of ci:ansing worldwide especially in developing markets.

Because of its popularity, abundance and economy soaps' use is extended beyond cleansing. One important application is as a gelling or solidifying agent in cosmetic compositions suck as sticks. High fatty acids soaps like sodium stearate and sodium behenate were shown to form excellent solid gel matrices in various higher alcohol solvents like Propylene Glycol. 42

There are 2 main ingredients for soap making: an alkali and an oil or fat. 43 Living tissues contain and synthesize oils, fats and waxes. The fatty materials found in seeds or coating of the leaves of certain plants and trees and as a body fat of animals are classified as esters which are the reaction product of carboxylic acid and an alcohol. Soap is manufactured from these esters (triglycerides) via several Chapter II. Non-DBS Solid Gel Formers -Soap 28

processing routes outlined in Figure 14 using alkali to neutralize the fatty acids or

saponify the fats.

RCO-OCH2 I RCO-OCH

RCO-JH2

(Triglyceride)

Direct Sa onification Fat Splitting Ester Int rchange

l(3 NaOH) l(Steam) (MeOH)

3RCOONa + Glycerine 3RCOOH + Glycerine 3RC00Na + MeOH

(Soap) (Fatty Acid} (Methyl Ester)

(NaOH) (NaOH)

RCOONa + MeOH

Neutral Fat Fatty Acid Methyl Ester Saponification Neutralization Saponification

F1gure. 14. soap processmg. rou t es 41 Chapter II. Non-DBS Solid Gel Formers -Soap 29

An example of sodium soap gelled stick is shown on Table 5. Sodium soap like sodium stearate is partially soluble in lower dihydric alcohols like propylene glycol and glycerine. Commercial sodium stearate is not based on 100% stearic acid but a cut of fatty acids, which usually contains only 50% stearic acid.·'-'

Table 5. Sodium stearate-based stick44

INGREDIENT FUNCTION % w/w

Propylene Glycol Solvent 80.10

Water Co-Solvent 11.00

Sodium Stearate Gellant 8.00

Fragrance Perfume 0.80

Triclosan Deodorancy 0.10

Dyes Color q.s.

UV absorbers UV Protection/Light q.s. Stability Chapter H. Non-DBS Solid Gel Formers - Gelatin 30

2.2.2 Gelatin

Gelatin, a protein derived from the partial hydrolysis of collagen, a maJor structural and connective protein tissue found in skin and bones of animals.37

Structually, gelatin molecules contain repeating sequences of glycine-X-Y triplets, where X and Y are frequently proline and hydroproline amino acids

(Figure 15 a and b).

Thr Amino Acid Composition of Geldtin

Aspartic acid 6 % Glycine 27%

Other amino acids Prolin and Hyd roxypro Ii ne 1 ,... % Glutamic acid 25'% 1 0%

Figure 15a. Gelatin's amino acid composition~6 Chapter II. Non-DBS Solid Gel Formers - Gelatin 3 I

Grlalin Slruc lural Chain

CH 2 CHOH I CH 2 CH 2 CH 2 CH 2 I I CH2 N CH NH CH2 NH N CH

co NH co co CH co H co CH co co

R R

Gl~1cine Proline y Glycine X Hydroxyproline

Figure I Sb. Gelatin's structural chain.u;

These sequences are responsible for the triple helical structure responsible for gel formation by immobilizing water molecules. Cel formed by gelatins, are not as rigid as DBS and its animal origin has limited its use on personal care applications.39 Chapter IL Non.lJBS Solid Gel Formers-Fatty Alcohols and Waxes 32

2.2.3 Fatty Alcohols and Waxes

Fatty alcohols like Cetyl Alcohol and Stearyl Alcohol and waxes such as Camuba and Beeswax are the most commonly used as solidifiers to deodorant sticks and lipstick compositions. 45 The mechanism for solid gel formation is similar to that of soaps. The major disadvantage of using fatty alcohols and waxes is the poor clarity of the resultant stick and they cannot be used to form solid cleansing bar formulations since they impede foaming. Table 6 is a sample formulation of an

Antiperspirant Dry Stick using Stearyl Alcohol.

Table 6. Antiperspirant dry stick44

Ingredient ¾w/w Stearyl Alcohol 26.00 Octyl Palmitate 14.50 Dioctyl Adipate 14.25 Cyclotetrasiloxane 20.00 Aluminum Zirconium tetrachlorohydrex-GL Y 20.00 Arachidyl propionate 5.00 Wheat germ glycerides 0.25 Fragrance q.s. Chapter II. Non-DBS Solid Gel Formers-Fatty Alcohols and Waxes 33

Product applications of waxes are shown in Table 7 in a lotion stick composition using Ozokerite and on Table 8, which is a lip balm composition containing candelilla wax, beeswax and camauba wax. The lotion stick concentrate is used for conditioning and moisturizing rough areas of the skin. The lip balm composition provides regenerating and protecting properties.

Table 7. Lotion stick (Abitec}4 7

Ingredient o/ow/w

Capry lie/ capric/lauric triglyceride 15.20 Ozokerite 14.50 Soybean (and) Hydrogenated cottonseed oil 13.50 Ceresin 12.75 Propylene glycol 12.00 Glyceryl dilaurate 10.50 Isopropyl palmitate 5.55 Octyl isononanoate 5.25 C 12- 15 alkyl benzoate 3.70 Cety l dimethicone 3.20 Aluminum starch octenylsuccinate 3.10 Tocopheryl acetate 0.30 Ascorbyl palmitate 0.25 Niacin 0.20 Chapter II. Non-DBS Solid Gel Formers-Fatty Alcohols and Waxes 34

Table 8. Lip balm composition (Aarhus Oliefabrik A/S)47 Ingredient %w/w Vegetable oil (and) hydrogenated vegetable oil (and) 73.20 Candelilla wax Hydrogenated vegetable oil 13.00 Shea butter 2.00 Beeswax 7.80 Carnauba (Copernica cerifera) wax 3.80 Flavor 0.20

Mobil Chemicals presents a lipstick composition consisting of waxes as shown in

Table 9:

Table 9. Lipstick (Mobil Chemicals}47

Ingredient o/ow/w Pentaerythrityl caprate (and) caprylate (and) 28.40 heptanoate (and) adipate

Isopropyl myristate 17.00 Ozokerite 2.50 Candelilla wax 12.20 Carnauba wax 2.10 Beeswax 4.10 Petrolatum 4.60 Propylene glycol stearate 3.90 Propylparaben 0.20 Titanium dioxide# 328 15.00 D&C Red no. 6 Barium Lake 10.00 Chapter II. Advantage ofDBS 35

2.3 Advantages of DBS

2.3.1 Stability and Compatibility

While unstable in highly acidic media, DBS is stable in basic, neutral and slightly acidic media. DBS is thermally stable up to 15

2.3.2 Safety and Toxicity

DBS is generally regarded as safe material with very low toxicity ( oral LDso in rates > 2000mg/Kg). Additionally, eye irritation potential is 0 per in-vivo studies done. Use level to form solid gel matrices is less than 5 wto/o .. 48

2.3.3 Transparency of solidified matrix

DBS can form transparent matrices when gelled in polar solvents at the right concentration and temperature. 4 Figure 16 shows transparency of gelled solvents

PEG 200 and Propylene Glycol at different concentrations from 0 to 5%. It is Chapter II Advantage ofDBS 36

possible to read through a 1-cm thick stick when transparency is over 67% (TI: transparency limit).

80 ~ j TI - a 60 >-u• ~ £ .ao !II gz 20

0 l.S 2 3 .a S PERCE.YrAGE OF DISORBENE ~ PEG :DO ~ PROPYLE.'liE GLYCOL

Figure 16. Transparency of gelled solvent versus DBS concentration3 Chapter II. Disadvantages ofDBS 37

2.4 Disadvantages of DBS

2.4.1 Insolubility in water

DBS is practically insoluble m water because of the presence of two benzaldehyde structures along the sorbitol backbone. This limits its application in personal care product formulations, which are largely depended on water as the main base vehicle. This therefore requires replacement of water with polar solvents like propylene glycol and glycerin, which are know to be highly hygroscopic solvents. Matrices containing high concentrations of propylene glycol and glycerin are susceptible to syneresis. Syneresis is manifested by the adsorption of moisture on the surface of the matrix as it interacts with a high humidity environment.

2.4.2 High Temperature Dissolution

DBS, unlike soap, dissolves at very high temperature, often in excess of 1OCfC depending on the solvent or combination of solvents used. This results into higher energy cost and increased safety risks in manufacturing. Chapter II. Commercially Available Cleansing Bar Matrices 38

2.5 Commercially Available Cleansing Bar Matrices

2.5.1 Opaque Sodium Soap Bar

Sodium Soap bars are the most widely used and most economical of all cleansing bar available in the market. Typical soap bar composition is shown in Table 10:

Table 10. Typical baby soap composition49

Ingredient Function %w/w

Titanium Dioxide Opacifier 0.25-1.00

Mineral Oil Skin Conditioning 1.00-5.00

Disodium EDTA Chelant 0.25-1.00

Perfume Fragrance 0.25-1.00

Soap Base (80:20 Palm:Coconut Oil) Detergency q.s.

Soap is made into a bar form via a series of bar finishing processes with the prime component being soap chips produced from the soap manufacturing process presented in Figure 13 and 16 (fatty acid neutralization route). The wet soap produced from these series of reaction is subjected to a subsequent purification, drying and pelletization to make it into soap chips. Soap bar finishing process is a Chapter ll. Commercially Available Cleansing Bar Matrices 39

machine intensive operation, which requires mixing of soap chips with fragrance, colorants and opacifiers with subsequent milling, refining, extrusion and forming into a bar. Below is a flowchart (Figure I 6) of a typical soap bar finishing operations.

Dhfilltd rats taiz OINI Oil, + Fa1111ndOih IJHclling SGA ' + !leorhrd 1111. ondOiJs + ·:::::J . Forry Ac d Nt111rol Foti Speni Soop lyt ,; 5peor Ntutrcfiroflon Soeonilicot,on reormenr ·s.c· SCHV·H' ... Soap Lye ... OCA C .... ear Purified ~ Soop j Soop lye ..... :~J .-- ccuum S,oro Voc~um Spray - Soop lye "'l.'·"9 Ory,ng Evoeorotion J_ t ,. J. {I' m· ...... y .._.., + ...... O:rv Soop Soop C,u e J ..., P ,'le r1 Bors Glymiu

r--7 ...... I ?· foiltl~ lovndl Soop Glymine , -<; FinisMng litiis itlf - I] Min~ ·uc· 'LIC" I 'Gf'." A' ,, ~ ...... I ; + To1le1 Soop lo u-nd,y*J' t rinea So,1 Son Glyce 'ne Sin1~11cla1md1 8or11'l~nPs --- "SLB

Figure 17. Soap processing and finishing process (Mazzoni LB, Italy)50

G G

40 40

AMP

G G

TTI

G G

OH OH

REFI

l l

A EXTT!

& &

LL LL

......

NC NC

REFI

es es

Italy)S() Italy)S()

Efol Efol

Ma1r1<..

LB, LB,

Bar Bar

g g

111

I I

(Mazzoni (Mazzoni

line line

ab/e ab/e

MIXING MIXING

A A

y y

finishing finishing

J J

:. :.

i i

, , _. _.

Soap Soap

0111111erc,a

_ _

.I .I

· ·

s.moo s.moo

C C

•

• -

" "

1,, 1,,

t ll ll .

< <

u u

18. 18.

INr INr

JJ JJ

-r; -r;

Ao:al'

\ \

111:'Jl

W10lllr

6t1 6t1

·,' ·,'

~ ~

e.ut e.ut

DOSING DOSING

.....,C

IH.JL.lli!li.U1

WJI! WJI!

hapter hapter

.IOl:D .IOl:D

Figure Figure

so,.1, so,.1,

0 0 0 Chapter II. Commercially Available Cleansing Bar Matrices 41

Traditional sodium soap bars have been the standard for cleansing bars particularly on bar integrity, rinseability and cleansing until the advent of new technologies for better aesthetic appeal like those of transparent soaps and syndet bars for improved mildness on skin.

2.5.2 Translucent or Pearlized Bar

Translucent bars are principally sodium soap base bars containing clarifiers such as ethanol, propylene glycols and glycerine. They are manufactured the same way as opaque bars. These bar matrices have no added advantage over traditional opaque soaps other than aesthetic appeal. Examples of translucent bar are found in Table 13.

2.5.3 Transparent Soap Bar

The most common of the transparent soap bars are those consisting of sodium and triethanolammonium salts of fatty acids. Excess triethanolamine (about 30%) is added to provide transparency. Neutrogena has popularized transparent soaps with the Neutrogena Transparent Soap. The advantage aside from being transparent is mildness to skin and high rinseability. 51 Another transparent bar in the market are from compositions developed by D. Lambino (US Patent

5,728,663) assigned to Johnson & Johnson52 involving clear colorless soap bars Chapter II. Commercially Available Cleansing Bar Matrices 42

with superior lathering and discoloration resistance and marketed as Johnson' s™

Baby Clear Soap and Clean & Clear™ Soap. These bars claim exceptional mildness on skin especially for use on infants and those with sensitive skin.

These transparent products are shown in detail in Table 11.

Transparent soap bars are manufactured very differently from opaque soaps. The process52 involves reacting fatty acids with caustic soda and triethanolamine in a mixing kettle at 6<:fC. Excess triethanolamine is used to enhance transparency.

As soon as neutralization is complete as indicated by rise in temperature to about

80oC and the mixture turning clear, other ingredients like fragrance and chelating agent are added. The molten soap is then filled into moulds or trays and allowed to cool at ambient. The hardened soap is then cut and stamped into a soap bar.

2.5.4 Syndet Bars

Synthetic detergent bars or syndet bars are cleansing bars where the surface-active ingredients in the formula are primarily synthetic detergents. An example is

Dove from Unilever, which is composed of synthetic detergent sodium isethionate as the surface-active ingredient. A typical patented formula covering this detergent bar technology is presented in Table 11. 53 Chapter II. Commercially Available Cleansing Bar Matrices 43

Table 11. Patented syndet bar composition

Ingredient ¾w/w Sodium lsethionate 20.0 Sodium Laury lsulfosuccinate 16.0 Paraffin 19.0 Starch 8.0 Microcrystalline Wax 1.0 Coco fatty acid 2.0 Laurie diethanolamide 2.0 Dextrin 22.0 Water 10.0

Note that in the above formulation, wax along with starch and starch derivatives are used as structurant in the cleansing bar matrix.

A combination syndet bar (Lever 2000) has also recently been developed by

Unilever, which combines the properties of traditional soap and syndet bar plus an antibacterial. Details are shown in Table 13. Chapter II. Commercially Available Cleansing Bar Matrices 44

Table 12. Opaque soap bars

PRODUCT INGREDIENTS SOLIDIFYlNG AGENT

1. Palmolive Soap Sodium Palmate Sodium Palmate Sodium Palm Kernelate Sodium Palm Water Kernelate Fragrance, Palm Acid Palm Acid Palm Kernel Acid Palm Kernel Acid Sodium Chloride Titanium Dioxide Glycerin Chamomile Extract Tetradibutyl pentaerithrityl hyd roxyhyd rocinnamate

2. Lux Soap Sodium Palmate Sodium Palmate Sodium Palm Kernelate Sodium Palm Sodium Stearate Kernelate WaterFragrance Sodium Stearate Sodium Chloride Palm Acids Palm Kernel Acid, Stearic Acid Titanium Dioxide Sodium Etidronate, Tetrasodium EDTA Toco her I Acetate, Cl 42090 Chapter II. Commercially Available Cleansing Bar Matrices 45

Table 13. Transparent Soap

PRODUCT INGREDIENTS SOLIDIFYING AGENT

1. Pears Soap Sodium Palmate Sodium Palmate Sodium Palm Kernelate Sodium Palm Water Kernelate Fragrance, Palm Acid Palm Acid Palm Kernel Acid Palm Kernel Acid Sodium Chloride Titanium Dioxide Glycerin Chamomile Extract Tetradibutyl pentaerithrityl h drox h drocinnamate

2. Palmolive Natural Sodium Palmate Sodium Palmate Soap Sodium Palm Kernelate Sodium Palm Sodium Stearate Kernelate Water Sodium Stearate Fragrance Palm Acids Sodium Chloride Palm Kernel Acid Palm Acids Stearic Acid Palm Kernel Acid Stearic Acid Titanium Dioxide Sodium Etidronate Tetrasodium EDT A Tocopheryl Acetate Cl 42090 Chapter II. Commercially Available Cleansing Bar Matrices 46

Table 14. Transparent Soap

PRODUCT INGREDIENTS SOLIDIFYING AGENT

1. Neutrogena Soap TEA-stearate Sodium Cocoate Triethanolamine Sodium Tallowate Purified Water Sodium Cocoate Glycerin Castor Oil Diethanolamine TEA-Oleate Cocamide DEA Fragrance Tetrasodium Etidronate

2. Johnson's Baby TEA-stearate Sodium stearate Clear Soap TEA-laurate Sodium laurate TEA-myristate Sodium myristate Sodium stearate Sodium laurate Sodium myristate Triethanolamine Purified Water Glycerin Mineral Oil TEA-Oleate Cocamide DEA Fragrance Disodium EDT A Chapter II. Commercially Available Cleansing Bar Matrices 47

Table 15. Syndet bars

PRODUCT INGREDIENTS SOLIDIFYING AGENTS 1. Lever 2000 Sodium tallowate Sodium tallowate Sodium cocoyl isethionate Sodium cocoyl . Sodium cocoate isethionate '!!! Water Sodium cocoate LEVER1' _.- - t:::::±:, Sodium isethionate Sodium '. ~1 Stearic acid isethionate Coconut fatty acid Stearic acid Fragrance Coconut fatty Titanium dioxide acid Sodium chloride Disodium phosphate Tetrasodium EDTA Trisodium etidronate BHT Active lngredient:Triclosan Sodium tallowate 2. Dove Beauty Bar Sodium tallowate Sodium cocoyl Sodium cocoyl isethionate, isethionate Sodium cocoate Sodium cocoate ' '/)01 (' Water Sodium Sodium isethionate isethionate Stearic acid Stearic acid Coconut fatty acid Coconut fatty Fragrance acid Titanium dioxide Sodium chloride Disodium phosphate, Tetrasodium EDT A Trisodium etidronate BHT Chapter III. Scope ofPresent Research 48

III SCOPE OF PRESENT RESEARCH

This research is aimed at assessment and optimization of physical performance properties and morphological characterization of DBS-solidified mild surfactant compositions in propylene glycol and glycerin for personal cleansing applications.

Specifically, this study covers the following areas:

1. Mixture Design Experimentation to develop predictive model equations for

each of the physical performance properties. This includes bar hardness, wear

rate, mush, foaming, transparency and syneresis.

2 Formulation optimization within boundaries set by the experimental design.

3. Comparison of physical performance properties of optimized formulation with

a commercial benchmark product.

4. Morphological determination of DBS in the matrix via Atomic Force

Microscopy and Freeze Fracture Transmission Microscopy

It is further the object of this research to gain understanding of how the physical performance properties of the solid matrix are influenced by the morphology of

DBS in the system. Chapter IV. Raw Materials 49

IV MATERIALS, METHODS AND DESIGN

4.1 Raw Materials

The cleansing bar matrix solidified by DBS is composed of the following raw materials: 1) polar solvents for the structural formation of DBS, 2)

Hydroxypropylcellulose, to increase solvent viscosity and act as a gelling synergist to DBS, 3) mild surfactants for detergency, and 4) Disodium EDTA for chelating heavy metal ions present in hard water. 3 Other ingredients for cosmetic appeal can be added like fragrance, colorants, moisturizers, and dyes. However, only the above major ingredients [1-4] have been incorporated in this study to simplify the experiment. The following provides detailed description of ingredients used in the cleansing bar matrix:

4.1.1 Polar Solvents

Propylene Glycol (1,3-Propanediol) was found to be one of the best

vehicles for structural formation of Dibenzylidene Sorbitol.'' It is a clear

colourless, water-white viscous liquid with a bitter taste but very low

toxicity (LDso rats, oral-30g/kg) making it harmless even as a food

additive. It reduces viscosity of the system and is used extensively in Chapter IV. Raw Materials 50

cosmetic formulations as a humectant, solubilizer for water-insoluble

components such as fragrances, colourants and preservatives, transparency

enhancer and anti-freeze. 54

Glycerin, while not as good as Propylene Glycol for dissolving DBS, was

used to partially substitute and therefore minimize use of Propylene

Glycol in the formula. Glycerin is preferred being more skin- and mucous

membrane compatible than Propylene Glycol. 54 Glycerin is found in

abundance in nature as a component of thousands of natural substances. It

is a colourless, viscous liquid, virtually non-toxic and easily digested and

unlike propylene glycol has a pleasant taste, which makes it an ideal

ingredient for both food and cosmetic products.

Propylene Glycol (DOW Propylene Glycol) and Glycerin (DOW

Glycerine 99.5% USP Grade) used in the experiment was sourced from

Dow Chemicals. Specifications are in Appendix 1-2 and typical physico

chemical properties are summarized in Table 16. Chapter IV. Raw Materials 51

Table 16. Typical physico-chemical properties of propylene glycol and

glycerin54

Propylene Glycol Glycerin

Freezing Point, vc Supercools <0 18.6

Boiling Point, UC 187 290

Specific Gravity @ 25UC 1.036 1.261

Viscosity @ 25UC, cP 44 954

Molecular Weight 76 92

Flash Point, °C 107 160

Refractive Index 20'C 1.4320 1.4746

Glycerine Propylene Glycol

Figure 19. Chemical structure ofglycerin and propylene g~col56' 57 Chapter IV. Raw Materials 52

4.1.2 Surfactants

Key to the performance as a cleansing system of the bar matrix solidified

by DBS is the incorporation of surfactants. This likewise distinguishes

this study from previous work where DBS cosmetic applications are

focused on solidifying deodorant and antiperspirant stick compositions.

The combination surfactant system developed in Johnson & Johnson3 was

used to include anionic, non-ionic and amphoteric surfactants to deliver

mild and effective cleansing in a bar form. The surfactant composition

solidified by DBS will be especially useful for infants and children and for

those adults with sensitive skin. 3

4.1.2.1 Anionic surfactants are manufactured and used in greater

volume than any other types of surfactants because of ease and low

cost to manufacture and is present in practically every type of

detergent. 56 Anionic surfactant molecule consists of a surface

active part which carries a negative charge and has a long chain

hydrophobe carrying the negative charge.56 The four most

common types of anionics used in shampoo formulations are

carboxylates, sulfate, sulphonate and phosphates. General structure

are shown in Figure 20. Chapter IV Raw Materials 53

RCoo· Na+ ROS02ff Na+

Carboxylate Su/fate

RS020- Na+ ROPO(OH)ff Na+

Sulfonate Phosphate

Fig 20. General chemical structure of anionic surfactants

The anionic surfactants used in this study consist of Sodium Laureth

Sulfate (Empicol ESC 70) from Huntsman and Sodium Laureth-13

Carboxylate (Miranate LEC from Rhodia). Material Specifications

are in Appendix 3-4 and Chemical structure are shown in Figure 21

below:

Sodium Laureth Sulfate:

Sodium Laureth- 13 Carboxylate:

Ol3 (CH2) 100li(OCH2CH2)uOCH2COONa

Figure 21. Chemical structure of anionic surfactants used57 Chapter IV. Raw Materials 54

4.1.2.2 Nonionic surfactants are surfactants that do not have a charge

group and at pH neutral and alkaline, where they are normally used, their

water-soluble, surface active group does not ionize to an appreciable

degree. 56 Nonionic surfactants are generally not good detergents or

foaming agents but play a secondary role to anionic surfactants because of

their mildness. 58 Nonionic surfactant used in this study is Termul 4280

(PEG-80 Sorbitan Laurate) sourced from Huntsman. Material

Specifications are in Appendix 5. PEG-80 Sorbitan Laurate belongs to the

class of Sorbitan Esters conforming to the structure in Figure 22.

Figure 22. Class chemical structure of sorbitan este..5 7

4.1.2.3 Amphoteric surfactants have both positive (cationic) and

negative (anionic) groups. In acidic solution, they form cations, m Chapter IV. Raw Materials 55

alkaline they form anions, and at neutral pH, form zwitterions (molecules

with 2 ionic groups of opposite charges).'' Amphoteric surfactants are

important because they are compatible with all other types of surfactants,

low skin and ocular irritation potential, and provides some conditioning

benefits. 60 Amphoteric surfactants used in this study consist of

Cocamidopropyl betaine from Goldschmidt (Tegobetaine L 7) and Laurie

Immidazoline Betaine from Huntsman (Empigen CDL 30/J). Material

Specifications are found in Appendix 6 and 7.

Cocamidopropyl betaine:

0 CH 2CH 2DH II I CH 3 (CH 2 ) 10 C- NHCH 2CH 2NCH 2COONa

Sodium Lauroamphoacetate:

Figure 23. Chemical structure of amphoteric surfactants use

4.1.3 Gelling Synergist

Hydroxypropyl Cellulose a non-ionic organic solvent soluble cellulose

ether was shown to help reinforce formation of Dibenzylidene Sorbitol by

increasing solvent viscosity. 56 Figure 24 provides an idealized structure

for a portion of HPC polymer with Molar Substitution of 3.0.

OH I OC~,CHCH,

-o

I"! OCH1CHCrl1 I OH

Figure 24. Idealized structure ofHPC, Molar Substitution= 3.059

HPC has excellent solubility in water and Propylene Glycol but only very

slight solubility in Glycerin. Solutions containing Hydroxypropyl

Cellulose are transparent, smooth and free from fibers. Solution behavior

is non-Newtonian since viscosity changes with shear rate. 59 The grade of

Hydroxypropyl Cellulose used in this study is Klucel Type HF grade from

Aqualon. Material Specifications are in Appendix 8. Chapter IV. Raw Materials 57

4.1.4 Chelating Agent

Disodium EDTA (Versene NA from Dow Chemicals) was used as

chelating agent to sequester water hardness. 60 Versene NA has Material

Specifications are in Appendix 9 and chemical structure is shown in

Figure 25.

Figure 25. Disodium EDT A chemical structure 61 Chapter IV. Test Methods for Physical Performance Properties 58

4.2 Test Methods for Physical Performance Properties

The following test methods were developed for the purpose of evaluating the critical physical performance properties of the cleansing bar matrices. These properties include bar hardness, mush, wear rate, foaming, transparency and syneresis. 63 -6 8

4.2.1 Bar Penetration

4.2.1.1 Scope and Purpose This method was used to measure depth of penetration into the solid or semi-solid matrix using a Penetrometer.

4.2.1.2 Principle of Method The Bar Penetration method was used as indication of bar hardness by its resistance to penetration. Hardness is one of the key aspects of soap bar integrity in use.

4.2.1.3 Equipment A Universal penetrometer was used to provide direct and precise

penetration measurements of solid and semisolid materials. Model H1200

consists of 5" diameter indicator dial, graduated in 400 divisions of

0.1mm, corresponding to 40mm penetration. Zero preset to eliminate Chapter IV. Test Methods/or Physical Performance Properties 59

errors. [ncludes 47.Sg plung:r with 3.2mm hol e, and two loading weights

(50g and I 00g).

Figure 26. Penetrometer equipment-product set-up Chapter IV. Test Methods for Physical Performance Properties 60

4.2.1.4 Sample Preparation

Specimen bars were conditioned at ambient (25°C ± 2°C) for at least 4

hours prior to testing. Moisture and dirt were removed and the surface

smoothened prior to testing.

4.2.1.5 Procedure

The bar specimen sample was placed on the base of the unit and directly

under the plunger. The lock screw was released and the height of the

mechanism head adjusted until the point of the penetrating instrument is

exactly in contact with the surface of the sample. Coarse adjustment was

made by means of the coarse adjusting screw and the head was securely

locked by means of the lock screw. The plunger is released for 1 second

to penetrate the bar. The depth of penetration was read by gently pushing

the depth gauge rod downward as far as it will go. The dial reading

indicated the depth of penetration in one tenths of millimeters.

The above procedure was repeated 2 times in another area of the bar

surface ± 5 mm from the center and the mean penetration reading

recorded. Chapter IV. Test Methods for Physical Performance Properties 61

4.2.2 Bar Mush

4.2.2.2 Scope and Purpose

The method was used to determine the amount of mush formed by a

cleansing bar matrix.

4.2.2.1 Principle of Method

Soap bars in particular, generally absorb water when left in wet soap dish

after use. The soap in contact with water produces a gelatinous material,

called soap mush, which is readily removed during subsequent use of the

soap. Soap mush affects the overall economy of the bar.

4.2.2.3 Apparatus

Petri Dish Bottom, Triangular holder, 50mL Graduated Cylinder

4.2.2.4 Sample Preparation

Soap bars were preconditioned to 25°C ± 1'C for 1 hour prior to testing.

4.2.2.5 Procedure

50 mL of purified water is added on a petri dish bottom containing a

triangular soap holder placed at center of the dish (Figure 27a). The Chapter IV. Test Methods for Physical Performance Properties 62

triangular soap holder provided support to the soap bar while in contact

with water.

The initial weight of the bar was reccrded after preconditioning. The bar

was then placed on top of the petridish bottom and remained in contact

with water for 16 hours (Figure 27b). The bar was then lifted from the

dish and the mush removed by scraping (Figure 27c). The soap mush that

was removed from scraping was left in the petri dish. The scrapped bar

was then dried at 25°C ± t>C for 4 hours and the final weight of the bar

was subsequently recorded.

Figure 27. Soap mush test procedure (Steps a to c, clockwise) Chapter IV. Test Methods/or Physical Performance Properties 63

4.2.2.6 Calculation

Initial Weight - Final Weight % Mush = x100% (Equation 4.2.2) Initial Weight

4.2.3 Foam Volume Tumbling Tube

4.2.3.1 Scope and Purpose

The method was used to detennine the volume of foam generated by a

solid to semi-solid cleansing matrix.

4.2.3.2 Principle of Method

Lathering 1s one of the most important attributes of a cleansing bar

perceived by the consumer. Soap bars when wet require friction to

generate lather. The tumbling tube apparatus through rotation was used to

closely simulate foam generation of bar in-use.

4.2.3.3 Apparatus

Foam volume of bars were measure using a tumbling tube apparatus from

the Newton Instrument Company, Ltd. (UK) shown on Figure 28. The Chapter IV. Test Methods for Physical Performance Properties 64

apparatus is made up of holder for 1-Liter graduated cylinders, which are

attached to a rotating shaft with variable speed and number of rotation.

Figure 28. Foam volume tumbling tube equipment

4.2.3.4 Sample Preparation

1cm x 2cm x 2cm specimen bar of approximately 5g weight was cut and

actual weight recorded. Water with hardness of 4-Sgrains/ga llon at

temperature of 26-28°C was prepared. Chapter IV. Test Methods for Physical Performance Properties 65

4.2.3.5 Procedure

Each of the 6 cylinders was filled with 100mL water and loaded with test

bars in their designated cylinders. The lead of each cylinder was closed

and secured in the tumbling tube holder. The cylinders were rotated 50

times at 20 rpm. Foam height is then measured after the cylinders were

allowed to stand for 1 minute.

4.2.3.6 Calculation

Measure and calculate foam height as:

Foam Height = Height of dense foam

- Height of Soap solution (Equation 4.2.3)

4.2.4 Bar Wear

4.2.4.1 Scope and Purpose

This method was used to determine the wear rate of a wet cleansing bar

matrix when subjected to friction simulating rubbing action during use. Chapter IV. Test Methods for Physical Performance Properties 66

4.2.4.2. Principle of Method

Bar wear is the numerical expression of a portion of the consumer

perceived bar economy. Technically, it translates directly from solubility

under mechanical abrasion.

4.2.4.3 Apparatus

The same equipment used in Foam Volume Tumbling Tube in Figure 28.

4.2.4.4 Product Preparation

1cm x 2cm x 2cm specimen bars of approximately 5g weights were cut

and actual weight recorded. Water with hardness of 45grains/gallon at

temperature of 26-28°C was prepared.

4.2.4.4 Procedure

· After measuring the foam height from the tumbling tube apparatus, the

specimen bars from each of the cylinder were removed and allowed to drain

and dry at ambient for a minimum of 4 hours. The final weight of the bar is

then recorded. Chapter IV. Test Methods for Physical Performance Properties 67

4.2.4.5 Calculation

Initial Weight- Final Weight lOOo/c (E . ) o/co Bar W ear= x o quatmn 4. 24 Initial Weight

4.2.5 Syneresis

4.2.5.1 Scope and Purpose

This method was used for the determination of syneresis as measured by the

amount of moisture adsorbed per exposed surface area of the cleansing bar

matrix.

4.2.5.1 Principle of Method

Syneresis is the amount of moisture adsorbed from humid air, which has

accumulated on the surface of the bar while approaching equilibrium

moisture concentration over a period of time.

4.2.5.3 Equipment

CAT 1800G SL Cooled Stability Incubator from Contherm Scientific

Limited was used as Humidity Chamber to test for syneresis (moisture

absorption) of the samples at 40 °C and 75% RH. 68 Chapter [Y. Test Method5for Physical Pe,jormance Properties 68

The chamber consists of high quality stainless steel interior, full fiberglass

insulation, with non-jar magnetic door catches and corrosive-resistant

epoxy powder coated exteriors. It is fitted with mechanical convection

fan system and safety features involve fitting with an independent user

adjustable Hi-Limit completely separate from normal conditions.

Figure 29. Humidity chamber

4.2.5.4 Product Preparation

Molten product was poured into a polypropylene mould measuring 85mm

x 40mm on the surface and depth of 20mm. The specimen samples in the

moulds were then allowed to cool in a dessicator at 2S'C ± 2°C for 4

hours. Chapter IV Test Methods for Physical Performance Properties 69

4.2.5.5 Procedure

Each of the moulds containing the specimen bar was weighted and then

transferred into the Humidity Chamber for exposure to 75% humidity and

40°C. Specimen samples were removed at different time intervals and

weight recorded.

4.2.5.6 Calculation

Syneresis at a particular period of time is calculated as:

Syneresis = Weia=ht - Final Weia=ht Ca=l (Equation 4.2.5) 40mmx85mm

4.2.6 Transparency

4.2.6.1 Scope and Purpose

This method was used to determine the degree of transparency by ranking

versus a standard and as measured using UV-visible Spectrophotometry.

4.2.6.2 Principle of Method

To obtain the relative transparency of a specimen sample versus a

standard, a method of grading transparency was used with O = totally Chapter IV. Test Methods for Physical Performance Properties 70

transparent to 10 = totally opaque. For absolute measurement of

transparency, the amount of light absorbed by a sample at a specific

wavelength to that absorbed by a blank sample is compared.

4.2.6.3 Equipment

For absolute transparency measurements, the UV Visible

Spectrophotometer was used. The instrument compares the amount of

light absorbed by a sample at a specific wavelength to that absorbed by a

blank sample.

4.2.6.4 Procedure

Test samples consisting of molten bars were placed in transparent cuvettes

and allowed to cool and harden at 25°C ± 2°C. Each of the cuvettes

containing the samples was subjected to UV Visible Spectrophotometry

for % Transmittance and also graded by expert panelist as to degree of

transparency. Cuvette containing purified water was used as the blank or

standard sample. % Transmittance is calculated as:

% T = 100 (I/lo) (Equation 4.2.6a) Chapter IV. Test Methods for Physical Performance Properties 71

Where:

T = Transparency

I = intensity of light beam after leaving the sample

lo = intensity of light before entering the sample

Relative degree of transparency is calculated by taking the mean of three

expert panel grading

Mean GT = GT 1 + GTi+ ... GTn (Equation 4.2.6b)

Where:

GT= Transparency grading

n = number of expert panel grading Chapter IV. Test Methods for Morphological Characterization 72

4.3 Test Methods for Morphological Characterization

4.3.1 Atomic Force Microscopy (AFM)

4.3.1.1 Scope and Purpose

The atomic force microscope (AFM) was used to gmerate topographic

images of the surface of the cleansing bar matrices under study.

4.3.1.2 Principle of Methocf9

AFM was used to probe the surface of the bar specimen via a sharp tip, a

couple of microns long and around 10-60 nm in diameter. The tip is

located at the free end of a cantilever that is 100 to 200µm long. Forces

between the tip and the bar specimen surface cause the cantilever to bend,

or deflect. The measured cantilever deflections allow a computer to

generate a map of surface topography. The diagram in Figure 30

illustrates how it works. As the cantilever flexes, the light from the laser is

reflected onto the split photo-diode. By measuring the difference signal

(A-B), changes in the bending of the cantilever can be measured. Chapter IV. Test Methods for Mo,phological Characterization 73

Figure 30. AFM principle.69

4.3.1.3 Equipment7°

Figure 31a. AFM equipment set-up Chapter [V. Test Methods for Morphological Characterization 74

Basic SPM Component

Microscope Computer

)( y Olgltsl Scnnnor Signal ~ l=>toceaaor

z Conltollt!r I- !!l&ctronlcs (An~log 11,terllice ~-~"-+---"< ;c 1ectronlcs1 1--;-...;___ __, Probo Dot ctor ~ 1 I , . ••••. < 11niplc

Vlllr l ion l!

Figure 31b. Basic scanning probe microscopy components70

4.3.1.4 Scanning Probe

Scanning probe used in this test is the Olympus Oxide -Sharpened Silicon

Nitride, which is excellent fo r scanning in a tapping mode.

4.3.1.5 Sample Preparation

About I g of sampl e was wetted in water overnight and allowed to dry in a

microscope slide to constant weight at I 05°C. This is to re move Chapter IV. Test Methods for Morphological Characterization 75

superficial solvent by saturating with water and then drying surface of the

sample.

4.3.1.6 Procedure 70

Contact Mode

Samples were first subjected to contact mode interaction between the tip

and the sample. Contact mode AFM operates by scanning a tip attached

to the surface of a cantilever across the sample surface while monitoring

the change in cantiever deflection with a split photodiode detector. The tip

contacts the surface through the adsorbed fluid layer on the sample

surface. The surface of the sample is in close contact with the tip as the

scanning proceeds. However, because of the existence of large lateral

forces on the sample as the drip is dragged over the specimen, the

topographical image produced was not very clear. Hence, tapping mode

was used instead to scan the surface of the bar specimen.

Tapping Mode

In the tapping mode, the cantilever was oscillated at its resonant frequency

with amplitude ranging from 20nm to 100nm. The frequency of

oscillation was at the side of the resonant frequency. The tip lightly taps Chapter IV. Test Methods for Morphological Characterization 76

on the sample surface during scannmg, contacting the surface at the

bottom of its swing. The feedback loops maintains a constant oscillation

amplitude by maintaining a constant RMS of the oscillation signal

acquired by the split photodiode detector.

4.3.2 Freeze Fracture

4.3.2.1 Purpose and Scope

Freeze fracture transmission electron microscopy (FF- TEM) was used to

determine the sulrmicron structures in the bar soap formulations.

4.3.2.2 Sample Preparation

A 0.25mm thick sample of the cleansing bar was mounted between thin

metal sheets and rapidly cooled with liquid propane to - l 96°C. The

sample was then transferred under liquid nitrogen to a pre-cooled cold

stage of a Balzers BAF-301 high vacuum freeze-etch unit (Techno Trade

International, Lichtenstein). The sample was fractured at the low

temperature and etched at - l 5

fracture faces were shadowed at an entire fracture surface to create Chapter IV. Test Methods for Morphological Characterization 77

selective electron contrast. A thin layer of carbon was deposited over the

entire fracture surface to create a continuous replica.

4.3.2.3 Imaging Technique

The replicas were then examined usmg a JEOL I OOCX2 electron

microscope (Japanese Electronic Optical Laboratories, Japan). Chapter IV. Experimenlal Procedure 78

4.4 Experimental Procedure

The principles and statistical techniques of Mixture Design of Experiment1• 72 or

MOE were used to develop and optimize the cleansing bar formulation matrix on the basis of preferred physical performance properties. MDE was used in lieu of trial and error and single variable experimentation approach traditionally used in developing formulations. The experimental program is summarized in the diagram in Figure 32.

DEFINE EXPERIMENTAL OBJECTIVES • Develop predictive model equatio ns • Optimize formulation • Compare, otimize fonnulation to benchmark ~ ~ SELECT CRITICAL PROPERTIES CHOOSE INGREDIENT CONCENTRATION RANGES • Hardness • DBS • Wear • HPC • Mush • Glyceri.n • Foam • Propylene glycol • Transparency • Syneresis

FINALIZE MIXTURE DESIGN + • D-optimal Design

CONDUCT EXPERIMENT MEASURE PROPERTIES • 18 of20 fonnulations successful. • Methods development • Measurements Chapter IV. Experimental Procedure 79

ANA YLZE AND OPTIMIZE • Analyze predictive models for fit. • Effect of ingredients and combinations in each of the physical perfonnance properties. • Optimum levels and combination of ingredients to achieve desired perfonnance properties.

VALIDATE RESULTS • Test model equations by fonnulating optimum fonnulations suggested by MOE.

Figure 32. Summary of mixture design experimental program

4.4.1 Objectives of the experiment

Earlier work of the author has identified the key ingredients that comprised the base cleansing bar matrix. This involved prior screening of ingredients on the basis of safety, performance and quality. The tcehnology of DBS-solidifed gel antiperspirant and deodorant sticks formulations was used in gelling the solvent surfactant system to make a solid cleansing bar matrix. This experiment was conducted to:

a) Develop predictive mathematical models for each of the bar physical

performance properties,

b) Analyze effects of the ingredients and combinations, thereof on each of

the bar physical performance properties, Chapter IV. Experimental Procedure 80

c) Determine optimum ingredient level and combination based on the

mathematical models for each of the physical performance properties.

d) Compare performance versus a commercial product benchmark.

4.4.2 Identification of Critical Cleansing Bar Properties

Table 17 illustrates the response variables, which are the cleansing bar physical performance properties that were identified as critical to the acceptance of the product by the consumer. Because the base formula matrix is a new technology, there was no commercial benchmark available. In the absence of a technology benchmark, Johnson's Baby Clear Soap was used being glycerin-based, mild on skin and transparent. Likewise, it has performance limitations like syneresis, which is similar to the DBS solidified matrix but non-existent in traditional opaque soap bars. Table 17. Bar properties, benchmark, criteria and optimization goal

PHYSICAL PERFORMANCE TEST METHOD ACCEPTANCE OPTIMIZATION PROPERTY CRITERIA RELATIVE GOAL TO BENCHMARK

1. Bar Hardness Bar Penetration Parity Minimize

2. BarWear Bar Wear Rate Parity Minimize

3. BarMush Bar Mush Test Parity Minimize

4. Syneresis Moisture Adsorption in Parity Humidity Chamber Minimize

5. Foaming Foam Tumbling Tube Parity Maximize

6. Transparency Grading Scale Preferably transparent Within defined range Chapter IV. Experimental Procedure 82

4.4.3 Identify Ingredients Range of Concentrations

Table 18 shows variable ingredients that were critical and those fixed ingredients that were not critical in the mixture design of experiment. The ingredient concentrations were set based on ingredient limitations by virtue of its physico chemical properties and its known compatibility and incompatibility with the other ingredients in the matrix. The level of surfactants was fixed to maintain the combination that was shown on previous work in Johnson & Johnson to have both low ocular and skin irritation. Likewise, the chelant (Disodium EDTA) level was fixed since practical range of concentration in the fonnula is believed not to have significant impact on perfonnance.

In a mixture, the proportions of each ingredient must add up to one. Hence in the case of this fonnulation, the ingredient concentrations should sum up to 100%.

Likewise, it was observed from screening experiments that HPC does not swell in glycerin but can effectively swell in propylene glycol at 2% maximum concentration. At higher concentrations of HPC, the mass becomes too thick to evenly disperse DBS in propylene glycol. Therefore, the mixture and HPC solubility limitation translates to two mixture design constraints: Chapter IV. Experimental Procedure 83

Mixture Total Constraint: A+B+C+D = 74.71 (Equation 4.4.1)

HPC Solubility Constraint: B- 0.02C > or = 0 (Equation 4.4.2)

From Equation 4.4.2 it can be inferred that HPC can c

0.50 0.50

25.19 25.19

TARGET TARGET

5 5

4 4

50 50

74.31 74.31

HIGH HIGH

(w/w%) (w/w%)

0 0

0.50 0.50

15.31 15.31

LOW LOW

(w/w%) (w/w%)

range range

Fixed Fixed

GOAL GOAL

In In

Minimize Minimize

Maximize Maximize

Component Component

Gellant Gellant

synergist synergist

Solvent Solvent

Chelant Chelant

Detergency Detergency

Gelling Gelling Principal Principal

FUNCTION FUNCTION

Ingredients Ingredients

Fixed Fixed

cellulose cellulose

Sorbitol Sorbitol

glycol glycol

mixture mixture

EDTA EDTA

and and Variable

INGREDIENT INGREDIENT

Glycerin Glycerin

Hydroxypropyl Hydroxypropyl

Propylene Propylene

Dibenzylidene Dibenzylidene

18. 18.

Surfactant Surfactant

Disodium Disodium

D-

C-

B-

A- Table Table Chapter IV. Experimental Procedure 85

4.4.4 Mixture Design Selection

Stat-Ease Design Expert-6 Beta Version Software was used as statistical tool. 73

Several Mixture Designs are available but Doptimal design was selected since ingredient ranges are not the same and the mixture design has 2 constraints as shown in Equations 4.4.1 and 4.4.2. The design met all evaluation criteria:

4.4.4.1 No Alias found

The selected D-optimal design was found to adequately estimated the

coefficient for the desired model. Since the design did not result to too

few points nor picked the wrong points, the estimated model terms are not

considered aliased. Moreover, there were enough unique design points to

estimate all the coefficients for the chosen quadratic model.

4.4.4.2 Degrees of Freedom

The d-optimal design was a good design since it resulted to lack-of-fit

degrees of freedom = 3 and pure error degrees of freedom = 5. Larger

degrees of freedom increase the discrimination between adequate and

inadequate models. Chapter IV. Experimental Procedure 86

The D-optimal mixture design recommended a total of 20 experiments to be conducted and a quadratic model was suggested. Table 19 provides the summary of experimental design data with respective component combinations.

Table 19. Experimental design data Std Run A B C D Number (DBS) (HPC) (Glycerin) (Propylene Glycol) 4 1 5.00 0.00 0.00 69.71 10 2 2.38 0.00 20.08 52.25 7 3 2.75 0.50 50.00 21.46 11 4 1.57 0.13 12.55 60.47 14 5 1.37 0.63 37.55 35.17 8 6 5.00 1.00 50.00 18.71 3 7 5.00 0.00 50.00 19.71 5 8 0.50 0.00 50.00 24.21 15 9 3.62 0.29 29.22 41.58 20 10 5.00 0.00 50.00 19.71 12 11 5.00 0.50 25.00 44.21 16 12 0.50 0.00 50.00 24.21 13 13 0.50 0.25 25.20 48.76 9 14 2.38 0.40 20.08 51.85 6 15 0.50 1.00 50.00 23.21 l 16 0.50 0.00 0.40 73.81 18 17 5.00 0.00 0.00 69.71 17 18 5.00 1.00 50.00 18.71 2 19 5.00 0.33 33.33 36.04 19 20 0.50 1.00 50.00 23.21 Chapter IV. Experimental Procedure 87

4.3.5 Experimentation and Preparation of Product Formulations

Each of the 20 formulations recommended by the d-optimal mixture design were made in I-Kg batches in a 1.5-liter beaker using a paddle mixer attached to a lightning mixer motor with speed of 100 to 350 rpm. Dataplate® Digital Hotplate equipped with a temperature probe was used for controlled heating.

The process of making the cleansing bar matrix divides itself into 7 steps as illustrated in Figure 33.

Figure 33. Processing steps in making cleansing bar matrix

STEPI

The required amounts of glycerine and propylene glycol were mixed at

l 50rpm and heated to 8Cf C ± 2°C. Chapter IV Experimental Procedure 88

STEP 2

As soon as solvent mixture temperature reached 80°C ± 2°c, mixing speed was increased to

200rpm and Hydroxypropyl

Cellulose was added slowly for better dispersion in the solvents.

STEP 3

Hydroxypropyl cellulose was mixed continuously until fully hydrated.

This is accomplished when the particles are fully swollen and the solution becomes clear. Chapter IV. Experimental Procedure 89

STEP 4

Temperature of the mixture was increased to l l 5- l 25°C and then

DBS was added into the mixture.

(Heating rate to reach this temperature range is not critical but should be slow and steady.)

STEP 5

Immediately after DBS was full y

dissolved, the surfactant-Disodium

EDT A premix was added into the

mixture. (the premix was pre-heated

to 80 °c ± 2°C prior to addition into

the mixture). Chapter IV Experimental Procedure 90

STEP 6

Molten stock was poured into

polypropylene moulds and allowed

to cool and harden at ambient air

temperature of 25°C ± 2°c.

STEP 7

As soon as the bar hardens, the polypropylene moulds were heat sealed with polyethylene-lined aluminum foil. Products were aged for I week prior to testing. Chapter V Results and Discussion 91

V RESULTS AND DISCUSSION

5.1 Mixture Design Analysis

18 of the 20 formulations from the mixture design experiment were successfully carried out. Two formulations were removed from the experimental design because of difficulty in completely dissolving DBS at the defined maximum concentration of 5% in glycerin within the temperature range of 110-125°C. With only half the concentration of DBS dissolved, viscosity of the solvent mix increased from 2,000 cps to 100,000 cps. This significantly reduced fluidity and prevented further dissolution of DBS. It was observed that temperature of 150°C and above was required to reduce solvent mix viscosity and completely dissolve

DBS. We did not progress the option of elevated heating to incorporate the two formulations in the design since temperature outside the operating range of 110-

125°C introduces process variable in the mixture design and is beyond the scope of this study.

Duplicate samples taken from each of the 18 experimental formulations were evaluated for the following bar physical performance properties:

a. Bar Mush

b. Bar Wear Rate Chapter V. Results and Discussion 92

c. Bar Hardness

d. Foam Volume

e. Transparency

d. Syneresis

(The above physical properties were earlier defined in Chapter IV under Section

4.2 - Test Methods for Physical Performance Properties.)

The mean value of each physical performance property is entered in the corresponding formulation run number in the mixture design worksheet (Table

20). The data were then processed using the Design Expert 6.0 software and from which predictive models were derived via statistical treatments.

1 1

4. 4.

7. 7.

4. 4.

ency ency

Transpar Transpar

I I

2sq 2sq

31~ 31~

31~ 31~ 21q 21q

24 24

Foam Foam

3.75! 3.75!

5.2~ 5.2~

5.5~ 5.5~

5.4~ 5.4~

6.1 6.1

Syneresisl Syneresisl

I I

SC, SC,

5.73 5.73

3.751 3.751

5.331 5.331

8.89 8.89

2.~ 2.~

Mush Mush

Bar Bar

I I

7.24 7.24

3.0~ 3.0~

5.7~ 5.7~

5.!~ 5.!~

17.0~ 17.0~

34.1~ 34.1~

Wear Wear

Bar Bar

I I

16 16

134J 134J

1351 1351

14 14

10~ 10~

13 13

26 26

27 27

15~ 15~

26 26

2~~ 2~~

27 27

26 26

27~ 27~

26 26

Bar Bar

Penetration Penetration

19.71 19.71

18.711 18.711

18.71 18.71

44.71 44.71 19.71 19.71

73.81 73.81

21. 21.

23.21 23.21

24.21 24.21

44.21 44.21 49~ 49~

34.4162 34.4162

Glycerin Glycerin

2d 2d

5 5

2d 2d

25. 25.

12.5495 12.5495

Glycol Glycol

33.46666 33.46666

0.392156 0.392156

Propylene Propylene

I I

1 1

d d

Worksheet Worksheet

o.d o.d

HPC HPC

I I

Design Design

~ ~

0. 0.

0. 0. 0.

0. 0.

2.7 2.7

DBS DBS

3.6187 3.6187

Mixture Mixture

I I

11 11

~ ~

101 101

1 1

20. 20.

No. No.

Run Run

Table Table

131 131

14' 14'

~~ ~~ Stdl Stdl Chapter V. Results and Discussion 94

Each of the physical performance property model equation was analyzed statistically and then validated to ensure that it adequately represented the true response. The following example on Bar Wear (Sections 5.1.1 to 5.1.4) illustrates the statistical techniques used to analyze each of the responses in the mixture design. Detailed statistical analysis of the other response variables are presented in Appendix 10.

5.1.1 Model Equation Selection

5.1.1.1 Model Fit

Design Expert® recommends the best model that can be fitted from our

response data. It can fit linear, quadratic, special cubic and full cubic

polynomials to the response. In the case of Bar Wear, special cubic and

full cubic cannot be estimated by the chosen design because they are

aliased (Figure 34). Aliased condition exists when there are fewer

independent points in the design than there are terms in a model resulting

in parameters that cannot be estimated independently. Under this

condition more experiments are required to cover the design space and to

be able to use models of the higher order. However, in this study, it was

found that a quadratic model is sufficient and no alditional experiment

was considered. Chapter V Results and Discussion 95

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0, Evaluation Bar wear rn Constrarns '" WARNIIIG: The Special Cubic Model is Aliased! m ii Analysis Penetratron(Analyzed) m WARHIHG: The Cubic Model is Aliased! 111

Bar Mush(Analyzed) Sequential Model Sum of Squares Moisture AbsorpllOl"(AnalyZt Foam VollMlle(Analyzed) Sum of Mean Transparencv(Analyzed) Source Squares OF Square Value Prob > F .I..' Oplmzation Mean 7485 98 7485 98 Numerical Linear 3460 45 115348 31 39 < 0 0001 Graptical Quadratic 381 70 63 62 383 00420 Suggested y Point Predrcbon Special Cubic 93 21 31 07 393 00875 Aliased Cubic 0000 Alrased Residual 39 54 7 91 Total 1146089 18 636 72

'Seqi;en1,,1 Model Sum of Squores" s.. ect lhe hrghest order polynomral where lhe addrbon&I terms are s1grnficant

,---- Ready

Figure 34. Fit Summary for Bar Wear

Figure 35 provides selection of one or combination of linear, quadratic, cubic model components. The default automatically selects the suggested model, however, model reduction was made as shown in analysis of variance since some of the terms were not statistically significant. Chapter V Results and Discussion 96

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~ en Cons!rairis Model ISc heffe .:J i Analys,s [.. J Penetral~Analyzed) Selection: fmll.:J L j L J Bar Mush(Analyzed) j ,... J Moisture Absorpl1or(Analyze 8 ,... J Foam Volurre(Analyzed) C ~ J Tr..-isparencl'(Analyzed) D Applicable terms but needs AB 1 Opt1m1zabon M AC M validation Numencal AD M Graphical BC M - Y Poi11 Predictoo 00 M co M ,a; AOO ACO Not applicable BCD "' (Outside scope: aliased) AB(A-B) "' AC(A.C) "' AD(A-0) "' BC(B-C) "' .:J

Ready

Figure 35. Model Term Selection Chapter V. Results and Discussion 97

5.1.1.2 Analysis of Variance (AN OVA)

ANOVA is a statistical tool for detecting 'the different sources of variations in the responses. It explains why responses vary as the settings of the components are changed. In the case of Bar Wear the quadratic terms terms AB, BC, BD, and

CD are not statistically significant since Prob > F value is greater than 0.05 which lies outside confidence limit of 95% (Figure 36). Only components and interactions with Prob > F values less than 0.05 will be included in the ANOV A.

Removing the non-significant terms results to a reduced model in Figure 37.

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Sum o1

!i:11111 1:t: ~1p 1,u 1ac nF ,, ••1, 11: f,u·, , F

·_;__•[.: ·-: · L •• ,I ~I.J. f t' . !I f.

• .:., ... CJ, • '·r, ·•::.=.,.: ;:·, .· ,

; ·.. ~ • :_;(J I

1-t1r ::•1. :1 .. :- J ,

; ~. ~ . ·~.. ,._ : ; ~;

..I.I _ ,

·-= ~•.l.d · ·.:.: 1:. · .:.:.d : ~···.,. .-., ,,.•

.... ~ !..,- :,,·

.-1 , .... -. I '

Figure 36. A NOVA for complete quadratic term Chapter V. Results and Discussion 98

·,.\.J11,'lubnrcdl \;.rn1er.ti\Ai.m l'.lir:1ttr. rtr.!t::;,u:.h\lJ ,~nn1 I ;,mbml')\~IJI \nm:rm.:iil.l r:31 h Ur.~1Qn I ~pc rl It IJ IJ : .... I_ 'r .:.c-~., [ · t'~ [_,i, ,, .:_-~:.r-T ~t· _-r ------,~ , ------~ 1..:a..,I "'*' lffll--*I

I, I 'J..., t j I I, .I•~"} I , ~. • , r_..,•.•. •, I . tll . a- :;;1.:rc: i1 ).f -~t.

M 511n ~( ·~ 1.:,. \ - rd,:-C"<. I Souroe Squairc V alJC Prct> " I j ~J ~ t " ' AM ,,., .A , 1.,. i. ,.., 1"11 •,; I • ii J I ~II,', ... ..1 ... , -;, ,•,,. 1 ol l i • }" . ,'1 . .., ,..r, .. ,..., '. ,...~.- -- ) 4 ~ , • • s... • J"." I ., .. ,: ·..· .1..--," ...... ,,,1 I< , ... _, C. -1~.;...i c:.1 ; __ :.;:•· :-· .- : •·.... : ~- •.• ~-·... •••• y

- > L ::1 . 1,·-t.:1..

, .. ~ , ....1~ ··<-Le e·~ .• - ,c~ :+- ~ .... , ~ ~ ~-. ,-,· ... .en r-,~c- ~-.., ·,

Figure 37. ANOVA with insignificant term removed

5.1.1.3 Diagnostics - Bar wear example

This section provides diagnostic tools to analyze residuals of responses and check

whether they satisfy the assumptions of randomness and normality. It helps detect

any undesirable pattern from residuals and suggest an appropriate transformation

to handle such pattern. [t is to be noted that in sections 5. 1. l.3. l to 5.1. l.3.9, the

same Bar Wear data results were plotted according to various statistical

treatments. Chapter V. Results and Discussion 99

5.1.1.3.1 Normal Plots.

Data appear normal as they fall along or close to the line.

Figure 38.

DESIGN- EXPERT Plot Bar wear Normal lot of residuals

99 a 95 90 a Normal% 80 / a Probability 7 0

30 a 20 a a 1 0 a 5 D

-1 7 8 - 0 . 90 -0.02 0 85 1. 73

Studentized Residuals

5.1.1.3.2 Residual versus Predicted Plot. The residual plot in Figure 39 is desirable since the points are spread evenly above and below the centerline. This plot is used to detect patterns of positive or negative relationships between the residual and the predicted value. Chapter V. Results and Disc11ss1011 100

DESIGN-EXPERT Plot Residuals vs . Predicted Figure 39. Bar w ear 3.00

D 1 50 D D Studentized D Residuals D a a n 0 .00 -" - - D a D a

-1.50 - a D

-3 .00

I I I I I 2 78 12 84 22 . 89 32 . 95 43 01

Predicted

5.1.1.3.3 Residual Versus Runs. The residual plot 1s acceptable since no residuals fall outside +/- 3 limits of the graph.

DESIGN-EXPERT Plot Figure 40. Bar wear Residuals vs . Run 3 00

a a a 1 50 -

Studentized D Residuals 0 D 0 . 00 - n n D - D - ll ll a - 1 50 - g a

-3 .00

I I I I I I I I I 9 1 1 13 1 5 1 7

X: Run Number Y: Studentized Residuals Chapter V. Results and Discussion l Ol

5.1.1.3.4 Residual Versus Factor. Figure 41 shows a desirable plot since the residuals are equally cluttered and scattered for all levels of each factor. This means that the residuals are not dependent on the level of each factor.

Figure 41. DESIGN-EXPERT Plot Bar wear Residuals v 3 00

a D D 1 5 0

Studentized 6 Residuals 0 00 D a D

. 1 50 a D

-3 oo -+------1

0 50 1 6 3 2 7 5 3 88 5 00

% DBS

5.1.1.3.5 Outliers. These are design points where the observed response does not fit the model. If a run has at-value greater than +3.5 er less than - 3.5, then it should be examined as a possible outlier.

DESIGN-EXPERT Plot Figure 42. Bar wear Outlier T 3 50

1 7 5 - a D D

D - D D 00 - " - a - - Outlier T D D D

7 5 - D a

- 3 50

I I I 7 1 1 1' 3 1' 5 1 7

Run Number Chapter V. Results and Discussion l 02

5.1.1.3.6 Cooks Distance. This is a measure of how much the estimated coefficients or parameters of the model would change if that particular run were omitted from the analysis. If the Cooks Distance for a run is less than l, the residual is not significant.

• DESIGN- EXPERT Plot Cook' s Distance FlgUre 43 • Bar wea r 1 00

0 75

Cooks Distance o 50

0 25 D IJ

Cl 000 -+---=--<.___ __.._~c'------l

9 11 1 3 1 5 1 7

Run Number

5.1.1.3. 7 Leverage. This refers to the potential of a run to influence the fit of the model. Leverage values close to l s hould be avoided. High leverage points should be replicated.

DESIGN-EXP ERT Plot Leveraae vs . R un Figure 44. Bar wear 1 0 0 -

0 8 3 -

0 . 6 7

50 Leverage - a a D IJ D a c D Cl Cl 33 w IJ a Cl D

0 1 7 - D CJ D

0 . 0 0

I I I I I I I I I 1 1 1 3 1 5 1 7

Run Number Chapter V. Resulfs and Discussion I 03

5.1.1.3.8 Predicted Versus Actual Plot. This shows how much prediction varies with respect to the actual observations. The ideal graph is where all points will follow the straight line. The graph for bar wear is acceptable.

DESIGN- E X PERT Plot Figure 45. Bar wear Predicted vs. Actual 44 7 2

3 4 a e

a Predicted Bar Wear 2 3 44

1 2 8 0

2 16

2 1 6 12 8 0 2344 3 4 08 447 2

Actual Bar Wear

5.1.1.3.9 Box-Cox Plot. Helps us determine the type of transformation that could be used on our data. No transformation required for Bar Wear.

Figure 46. DESIG N-EXPE RT P lot B a r w ear Box-Cox Plot for Power Transforms

Lambda 1 3 . 4 8 C urrent= 1

Low C . I. = 0 .22 High C .I . = 1 .38 1 1 . 4 4 Recommend tran sform: None (Lambda= 1 )

9 4 1

7 38

5 . 35

-3 -2 -1

X : Lambda Y : Ln(Res i dualSS) Chapter V. Results and Discussion 104

5.2 Predictive Model Equations and Graphical Analysis

Following are the predictive model equations for each of the physical properties derived from the mixture design experiment. Each of the model equation fits the response values adequately. This is indicated by very high regression R2 , which is an estimate of the fraction of overall variation in the data accounted for by the model.

MODEL EQUATION

2.61 7 5 4 Penetration l.57x10 A - l.26x10 B + 4.66x10 C 0.84 (Equation 5.2.1) + 4.29x10'D -.77xl0 5 AB - 2.33xl05AC-2.32xl05 AD

Ln (Bar Mush)= 19.87A + 0.05B + 0.065C + 0.0650 0.90 (Equation 5.2.2) - 0.46AB -0.29AC - 0.29AD

Bar wear= 134.91A - 11.68B + 0.50C + 0.69D - 0.80 (Equation 5.2.3) 2.03AC - 2.03AD Chapter V. Results and Discussion 105

MODEL EQUATION

Foam Volume = - 17.94A- 15.32B + 5.71C + 6.11D- 0.98 (Equation 5.2.4) 0.084CD

Transparency=+ l.31A- 0.07B - 4.SE-003 C + 0.050 0.93 (Equation 5.2.5)

Syneresis = - 0.30A + 244.60B + 0.08C + 0.07D - 0.78 (Equation 5.2.6) 3.29AB +o.0lAD - 3.34BC - 3.26BO

Where: A = % DBS, B = % HPC, C = % Propylene Glycol, D = % Glycerin Chapter V Results and Discussion 106

Model graph provides visual illustration on how the response behaves as the mixture blend or ingredient combinations are changed.

\\Jjpaubo,cdl \ptojecls\Asia Paciic Resea,ch\Danny Lambino\MDE\nmlfinal3.dx6 · Design-Expe,I 6.0.0 f ile Edil Y'.1ew Display Qptions Qesign,-,-.--,-,--,--,,------Tools !:!elp DI~I ~I ! l[t;lel ~IYII _J N~es for rvrrtf1nal3 ~--'------;;1 Design l rmfnr I.,.;.,.1 """ 111111 ' 1---e status

~- 0, Evaluation DESIGN-EXPERT Plot A DBS 55 6 ~ rn Constrons Bar wear :- jl Analysis Xl = A· DBS ;- j Perietratmn(Analyz, X2 = D: GLY X3 = C: PG ' j L. j Bar Mush(Analyzed • Design Po,nls

:- ) M01s1lle Absorption Actual Component L I FnRm Vt°W.R'Tlf'( naly B· HPC = 0.24 Fa dOls Tool .!!.l Anal~ aoo 18.71 f''-~ A.iJBS

73 97 a 50 55 26 D. GLY C PG Bar wear

Ready

Figure 47. Model Graph for Bar Wear Chapter V. Results and Discussion 107

5.2.1 Bar hardness

Penetration~u, = 1.57xl07A- 1.26xl05B + 0.84 (Equation 4.66xHfC + 4.29xl04D -.77xl05 AB - 5.2.1) 2.33xla5 AC- 2.32xl05 AD

The above model equation was transformed to a power equation as recommended by Design Expert Software to satisfy the equal variance requirement of the ANOVA and the equation provides a good fit with R =

0.84. Trace plot in Figure 48, and correlation analysis in Table 21 all point to bar hardness (penetration) being positively dependent on the concentrations of

DBS andHPC

DESIGN-EXPERT Plot Trace Pie el (Penetration)A2.61 280 Actual Components A: DBS= 1.16 B: HPC = 0.20 C: PG= 33.78 229.25 D: GL Y = 39.56

Penetration 178. 5

127.75

-0.296 -0.068 0.159 0. 3 8 7 0. 614

Deviation from Reference Blend

Figure 48. Trace plot for penetration Chapter V. Results and Discussion 108

Table 21. Correlation analysis of component versus response variable

COMPONENT

RESPONSE DBS HPC Propylene Glycerine VARIABLE Glvcol Penetration -0.85 -0.33 -0.25 0.33

Bar Wear -0.85 -0.45 -0.55 0.62

Bar Mush -0.90 -0.22 -0.24 0.33

Syneresis 0.10 -0.21 -0.44 0.42

Foam Volume -0.78 -0.37 -0.69 0.75

Transparency 0.89 -0.05 -0.11 0.01

5.2.2 Bar Mush

Ln (Bar Mush)= 19.87A + 0.05B + 0.065C Rz = 0.90 (Equation 5.2.2) + 0.065D - 0.46AB -0.29AC - 0.29AD

Bar mush model equation required transformation into a natural logarithmic equation because the residuals are a function of the magnitude of the predicted values. From the transformed equation, the relatively high coefficient of A versus other model terms in Equation 5.2.2 indicate that mush generated is reduced with increasing amount of DBS in the formulation. Chapter V. Results and Discussion 109

5.2.3 Bar Wear

Bar wear= 134.91A - 11.68B + 0.50C + 0.69D - RL =0.80 (Equation 2.03AC - 2.03AD 5.2.3)

Trace plot in Figure 49 illustrates bar wear decreasing sharply with only a slight increase in DBS and HPC concentrations from the reference blend.

This can be attributed to the increasing density of nanofibrillar percolation network formation at higher concentrations of DBS, making the bar less soluble and more resistant to mechanical abrasion. Detailed illustration of variations of this percolation network is shown in Section 5.4 using Atomic

Force Microscopy characterization techniques.

DESIGN-EXPERT Plot Trace Pie el Bar wear 44. 72 D Actual Components A: DBS= 1.24 B: HPC = 0.00 C: PG= 39.12 34 08 D: GLY = 34.35

23.44

12. 8

2 16

-0,705 -0.352 0.002 0.355 0.708

X: Deviation from Reference Blend Y: Bar wear Chapter V. Results and Discussion 110

DESIGN-EXPERT Plot Trace Pie el Bar wear 44. 72 C D Actual Components A: DBS= 0.50 B: HPC = 0.00 C: PG= 34.58 34.08 D: GL Y = 39.63 B

23.44

12.8

2.16

-0.613 -0.307 0.000 0.307 0.613

X: Deviation from Reference Blend Y: Bar wear Figure 49. Trace plot for bar wear at different ingredient combinations

5.2.4 Foam volume profile

Foam Volume = - 17.94A - 15.32B + 5.71C R' =0.98 (Equation 5.5.4) + 6.1 lD- 0.084CD

The amount of foam the bar generates is directly proportional to its solubility in the presence of mechanical stress. It was shown from these experiments that as the bar becomes more soluble, more surfactants were delivered into solution, which provided more foaming. Figure 50 shows how foam volume correlates with bar wear rate. Additionally, glycerin positively impacts on foaming because higher glycerin makes the bar more soluble partly due to lower allowable concentration of DBS and HPC that can be incorporated in Chapter V. Results and Discussion 11 1

the fonnula due to poor dissolution profile in glycerin (please refer to Figure

51).

FOAM VOLUME versus BAR WEAR RATE

500 ~------,

450 y • 4 .1947• + 212.18 R 2 • 0 .8421 J 400 - E w 350 ::!!: ::::, ..J 300 0 > ::!!: 250 <( 0 u.. 200

150

100 +++-HH-+++-++<>-+-+++-+-HH-+++-++->-+-+++-++<>-+-+++-++<>-+-+H-+++-.....-+-l 000 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 BAR WEAR(%)

Figure 50. Foam volume versus bar wear profile

DESIGN - E X PERT Plot

Foam Qty 440. 4 7 Actual Components A : D B S= 2 . 15 B : HPC = 0 . 30 c - PG = 23 . 98 382.853 D · GLY = 4828 Foa m Qty 325. 235

267. 618

210

-0 .503 - 0 . 260 - 0 .017 0 . 225 0 .468

Devi ati on from Reference B lend

Figure 51. Foam volume trace plot Chapter V. Results and Discussion 112

5.2.5 Transparency

Transparency=+l.31A-0.07B -4.SE-vv,C + 0.93 (Equation 5.2.5) 0.05D

The high concentrations of glycerin and propylene glycol in the formulation would normally yield transparent formulations. However, both DBS and

Glycerin were shown to negatively impact on transparency of the matrix.

Equation 5.2.5 along with trace plot in Figure 52 indicate linear relationship of the ingredient concentrations to the degree of transparency.

DESIGN-EXPERT Plot Trace Pie el A Transparency 8.36095

Actual Components A: DBS= 1.87 B: HPC=0.12 C: PG= 27.95 6.52071 C D: GL Y = 44.77

-0.410 -0.177 0.055 0.288 0.520

Deviation from Reference Blend

Figure 52. Transparency trace plot Chapter V. Results and Discussion 113

5.2.6 Syneresis

Syneresis = - 0.30A + 244.60B + 0.08C + 0.07D 0.78 (Equation 5.2.6) - 3.29AB +0.0IAD - 3.34BC - 3.26BO

It was observed from the mixture design experiments that syneres1s 1s prevalent in all of 18 solid matrices. This is attributed to the high concentrations of glycerin and propylene glycol in the formulation. To obtain a better understanding of the phenomenon as it occurs in the cleansing bar matrices, the following were investigated:

a) Effect of equilibrium concentration of moisture in the solvent and the

surrounding relative humidity b) Effect of hydroxypropyl cellulose capable of competitive hydrogen

bonding with propylene glycol and against moisture c) Effects of higher DBS concentration in minimizing inter-fibrillar gaps in

the solvent-surfactant matrix, contracting routes for solvent syneresis. Chapter V. Results and Discussion 114

5.2.6.1 Effect of equilibrium moisture coocentration

Syneresis tends to cease once equilibrium concentration of moisture in a hygroscopic substance and the surrounding relative humidity is reached. If the environment has higher relative humidity than a hygroscopic substance with which it is brought into contact, the substance takes up a predetermined amount of moisture, thereby bringing both relative humidities in equilibrium.

Syneresis in cleansing bar formulations if not properly controlled by formulation or packaging means could be a major drawback especially during transport and storage of the product.

To demonstrate this phenomenon, cleansing bar matrices with and without hygroscopic solvents were exposed to 60% relative humidity at 2~C for 45 hours. Figure 55 illustrates the relative degree of syneresis in the DBS solidified propylene glycol-glycerin-surfactants bar matrix (Bar A) to other cleansing bar matrices after 24-hour exposure.

Commercial Bar C is a traditional sodium soap that does not contain solvent as transparency enhancer and is not expected to produce syneresis on the surface.

Commercial bars B and D contains significant amount of hygroscopic solvent clarifiers in the formulation, which are capable of causing syneresis at very high humidity. Glycerin, a popular clarifier, absorbs moisture up to 21 % concentration at equilibrium with surrounding atmosphere at 50% relative Chapter V. Results and Discussion 115

humidity and 25 °C. Bar B (Johnson's Baby Clear Soap) contains 40% triethanolamine and 1% glycerin while Bar D contains more than 10% glycerin.

A. DBS-solidified Bar B. Johnson's Baby Clear Soap

C. Soap bar, no solvent D. Soap bar with Glycerine

Figure 53. Images of bars exposed to 60°/4, relative humidity and 2S''C for 48 hours

As illustrated in Figure 53, only Bar A (DBS-solidified solvent-surfactant matrix) exhibited syneresis. This can be explained by the proportionately higher amount of moisture (above 10%) in the commercial bar matrices versus Chapter V. Results and Discussion 116

below 1% moisture for the DBS solidified matrix m this study. Bar B contains 30% moisture while bar D contains 15%. At 60% humidity and

2~C, the commercial bar B and D contain significant amount of moisture in their matrices to have attained equilibrium moisture concentration and therefore no evidence of moisture uptake on the surface of the bar exists.

However, syneresis becomes inevitable in the solvent-surfactant matrix where the solvents are glycerin and propylene glycol at combined concentration of up to 75% with no free moisture content.

In this study, we have quantified syneresis via equilibrium hygroscopicity measurements over a period of time. It provides comparative hygroscopicity between formulations and indication on the rate of moisture gain while approaching equilibrium. Since the amount of moisture is a function of the exposed area-to-volume ratio, weight gained as a percentage of original weight is not used. Instead syneresis is measured as weight gain per unit area of exposed surface expressed in Equation 4.2.5 as follows:

. Initial Weight of Bar- Final Weight of bar Syneres1s = (Equation 4.2.5) Exposed Surface Area of Bar

Where Exposed Surface Area of Bar = 40mm x 85 mm = 3400 mm2 Chapter V. Results and Discussion 117

Samples are exposed inside a humidity chamber at controlled humidity and temperature and taken out at a designated time and weight recorded. Details of the procedure were presented in Chapter 4, Section 4.2.5.

Syneresis may be minimized with the addition of water in the formulations containing large quartities of hygroscopic solvents. The quantities should be sufficient to arrive at equilibrium in a given relative humidity. However, this may require large amount of water introduced into the formulation especially if moisture equilibrium at high humidity is required.

We have conducted an experiment to demonstrate the effect of adding free water in reducing syneresis of the DBS-solidified solvent-surfactant matrix. A

2 Kg batch of the matrix formulation in Table 22 was prepared following the procedure rescribed in Chapter IV Section 4.3.5.

Table 22. DBS-5olidified bar matrix formulation sheet INGREDIENT TYPE Weight% Weight (gram) SodiumLaureth Sulfate Anionic Surfactant 7.72 154.40 Sodium Laureth Anionic Surfactant 0.45 9.00 Carboxylate POE-Sorbitan Laurate Nonionic Surfactant 6.30 126.00 Cocamidopropyl betaine Amphoteric 8.64 172.80 Surfactant Chapter V. Results and Discussion 118

Lauroamphoglycinate Amphoteric 2.08 41.60 Surfactant Dibenzylidene Sorbitol Gelling agent 1.00 20.00 Hydroxypropyl cellulose Gelling synergist 0.75 15.00 Glycerin Solvent 22.96 459.20 Propylene Glycol Solvent 50.00 1000.00 Disodium EDTA Chelating Agent 0.10 2.00

The batch was then divided into 3 parts and into each part purified water was incorporated to make 0%, 6.5% and 12.5% free water accordingly. Samples with higher concentrations of free water were not included in the test since bar matrices are not formed at higher concentrations of free water.

The purified water was added in the molten matrix at 75-80°C at 200rpm mixing for 2 minutes. The amount and proportions of de-ionized water to bar matrix are summarized in Table 23.

Table 23. ¾ Free moisture of samples for syneresis test

Sample %Free Weight Purified Weight of Bar Water Water Matrix

Control 0 0 200g

Sample 1 6.5 13.00 g 187.00g

Sample 2 12.5 25.00 g 175.00g Chapter V Results and Discussion 119

The above samples in molten form are then poured into 40mm X 85mm X

30mm polypropylene moulds and allowed to cool and hardened inside desiccators to prevent moisture adsorption prior to subjecting to humidity exposure. Samples are then exposed inside a humidity chamber at controlled humidity of 75% ± 5% and temperature of 40°C ± 2°C and taken out at different time intervals up to 300 hours. Weight of the sample is recorded at each time interval and moisture adsorption calculated per Equation 4.2.1.

Moisture adsorption curves are shown in Figure 54. After 300 hours exposure, propylene glycol has already reached equilibrium moisture concentration

(Bmax) of 28g/34cm2 . The equilibrium moisture adsorption profile of propylene glycol is represented by Equation 5.4.1 and follows a rectangular parabolic or saturation binding curve.

Bmax • X Y= (Equation 5.3.1) ~+X

This equation describes the equilibrium moisture concentration as a function of time.

Where X = the time elapsed, hours

Y = the moisture adsorbed on the surface, g moisture/34cm2 Chapter V. Results and Discussion 120

Ket= is the equilibrium moisture constant

When time elapsed X is equal to Kd, the amount of moisture adsorbed on the surface of the sample is half the moisture adsorbed at equilibrium, Bmax.

After 300 hours exposure, it appears that glycerin and the sample matrices have not reached equilibrium moisture concentration. However, it is expected that they will follow the same equilibrium profile at much longer exposure periods. Equilibrium moisture equations for glycerin and the sample matrices have not been derived due to lack of data points.

Comparative moisture adsorption profiles of the sample matrices indicate that there is a proportionate reduction in moisture uptake with increasing free water content in the matrices. Likewise, the solid matrices have shown lower comparative moisture adsorption to pure glycerin and propylene glycol.

However, the magnitude of moisture reduction is not suffic ient to make the bar matrices acceptable. Moisture uptake on the surface of the bar still exists and increasing significantly within 24 hours exposure period, which is the normal exposure cycle time in actual usage of the bar during cleansing. The 24-hour period is already beyond 14 hours wherein half the equilibrium moisture adsorbed Kd of 14g/34cm2 is reached.

1 1

350 350

Water Water

Glycol Glycol

Water Water

300 300

• •

+ +

Free Free

X X

Free Free

5% 5%

Propyl~ne Propyl~ne

0% 0%

Glycerine Glycerine

• •

X X 6

+ +

250 250

~ ~

X X

. . •

I I

(Hours) (Hours)

200 200

~ ~

v v

• •

+ +

• •

+ +

Period Period

150 150

· ·

X X

• •

+ +

profile profile

Exposure Exposure

-----

100 100

~ ~

/. /.

adsorption adsorption

• •

~+ ~+

.• .•

• •

50 50

• •

~~ ~~

/.. /..

moisture moisture

I I

Kd Kd

scuss,on scuss,on

~ ~

rt:-

_ _

L L

and and

. .

I I

0 0

s s

+---1------

7 7

5 5

o, o,

o o

1 1

15 15

25 25

30 30

Comparative Comparative

. .

Resu

~ ~

c, c,

0 0

e e

Q) Q)

~ ~

-~ -~

M M -

N N

V V

Bmax Bmax

~ ~

0 0

t/) t/)

0 0

0 0 C: C:

1n 1n

~ ~

<( <(

"'C "'C

e:~201 e:~201

Figure Figure Chapter Chapter Chapter V Results and Discussion 122

Moreover, it is shown in succeeding paragraphs that incorporating water in the

DBS-solidified solvent-surfactant matrix introduces negative effects on bar appearance and physical integrity. Water from 10% in the DBS-solidified matrix was shown to decrease transparency and makes the bar softer.

For transparency measurements UV Visible Spectrophotometer was used and test method is described in detail in Section 4.2.6. Test samples consisting of molten bars containing 0% (control), 10% and 20% free water were placed in transparent cuvettes and allowed to cool and harden at 25'C. Each of the cuvettes containing the sample was subjected to UV Visible

Spectrophotometry for% Transmittance which is calculated as:

% T = 100 (I/lo) (Equation 4.2.6a)

Where I = intensity of light beam after leaving the sample

lo = intensity of light before entering the sample

Figure 55 provides comparative transmittance readings of samples indicating decreasing transparency with increasing moisture content. Since DBS is not soluble in water, it is possible that DBS µ-ecipitation from the solvent matrix occurs resulting to loss of transparency. This effect is studied in detail on succeeding section on DBS morphological evaluation. Chapter V. Resulls and Discussion 123

100

75 75 QI u C: IV ;:: 50 -E 1/) 50 C: ...IV 35 I-

0~ 25

None 10% 20% Free Water

Figure 55. Transmittance versus free water content

Figure 56 illustrates how bar hardness (in terms of penetration readings) is significantly affected by the amount of moisture incorporated in the matrix.

Penetration test method is presented in Chapter IV Section 4.2.1. The curve of Penetration as a function of % Free Moisture follows an exponential growth trend. Penetration readings increase in magnitude by a factor of l l 7.96e 0·0539X where X = % Free Moisture. At X = 0, Y is 117.96 which is the penetration reading at 0% free moisture. Chapter V Results and Discussion 124

450

400

350

-~ 300 ....0 y = 117.96e0.0539x 2,. 250 R2 = 0.9619 C: 0 :;; 200 "'... Cl) -C: Cl) 150 a.. 100

0 0 5 10 15 20 25 % Free Moisture

Figure 56. Penetration versus free water content

It is apparent that incorporating free water in the DBS-solidified solvent surfactant matrix provides some reduction on the degree of syneresis.

However, syneresis is still appreciably high and the resulting loss of transparency and reduced bar hardness may impact on the overall acceptance as a cleansing bar product. Further investigative work is required to determine how to incorporate water to reach instantaneous equilibrium concentration with the environment and without the negative effects on transparency and bar hardness. Chapter V Results and Discussion 125

5.2.6.2 Effect of hydroxypropyl cellulose in competitive hydrogen bonding with the glycols

Rheological additives were investigated with respect to their ability in gelling propylene glycol, the main solvent used in the cleansing bar matrix under study. These rheology modifiers come from 4 distinct types72 :

a) Natural Polymers: basically gums which are harvested directly or

derived from natural plants, microbial or animal sources,

b) Modified Natural Polymers: synthetic derivatives of natural gums,

c) Synthetic Polymers: synthesized from petroleum, or other

hydrocarbon-based raw materials and,

d) Inorganics minerals: either refined, naturally occurrmg ores or

synthetically produced.

Detailed classifications are in Appendix 11 indicating their solubility profile in propylene glycol. Among the rheology modifiers studied, hydroxypropyl guar and hydroxypropyl cellulose are found to be the most soluble and best viscosity builders in propylene glycol. Both viscosity modifiers can build viscosity in aqueous as well as polar solvents and were shown to improve hardness of anti-perspirant stick formulations solidified by DBS.

A constant humidity-temperature exposure experiment was conducted to determine effect of comparative levels of hydroxypropyl cellulose following the method described in Chapter IV Section 4.2.5. 0%, 0. 75% and 1.5% HPC Chapter V. Results and Discussion 126

were incorporated in the formula matrix and following the procedure described in Chapter IV Section 4.3. 5. Note that 3% in propylene glycol

( 1.5% in resultant matrix) is the maximum incorporation level of HPC.

Results show no significant difference in moisture adsorption profile with the addition of HPC as shown in Figure 57. It appears that it does not allow for competitive hydrogen bonding with glycols against water and therefore does not significantly minimize hygroscopicity of the system.

5.2.6.3 Effect of higher DBS concentration

Increasing the concentration of DBS in the matrix minimizes inter-fibrillar gaps resulting to a more densely packed DBS that may contract passageways for solvents to pick-up moisture. Note that moisture adsorption occurs at the surface of the bar and that increasing the density of DBS fibers in the matrix may decrease the amount of solvents exposed to the environment.

Results of dynamic hygroscopicity (moisture adsorption rate) measurements in

Figure 58, however, showed that even a threefold increase in the concentration of DBS in the formula (maximum concentration practicable), no significant reduction in moisture gain was observed. C h apt e r V Re.s u/J s a n d D 1s c 11ss 10 11 1 27

18 ------~-~~-~------16 •..

"C 14 • Cl) - -ee 12 ~ 0 (J ,.. "" ~; 10 • 0% HPC <( ~ :I • 0.75°/o HPC Cl)... -~- 8 ,~ :::::s 0 ,-.. 1.5% HPC -rn E 6 ,, ·-o- tn r". :!!: 4 -7'' 2 ,,"=

0 .., I I I 0 100 200 300 400 Exposure Period (Hours)

Figure 57. Moisture adsorption profile at different HPC concentrations at 60% relative humidity, 40"C

DBS DBS

2S 2S

1% 1%

3% 3%

• •

C C

400 400

4Cf 4Cf

, ,

humidity

I I

• •

300 300

relative relative

60% 60%

---

at at

(Hours) (Hours)

* *

DBS DBS

I I

3°/., 3°/.,

iii iii

200 200

Period Period

ii ii

versus versus

• •

% %

1 1

Exposure Exposure

I I

profile profile

100 100

• •

11 11

•• ••

s:'i

• •

adsorption adsorption

,~ ,~

• •

0 0

and and

0 0

8 8

2 2

4 4

6 6

Moisture Moisture

10 10

12 12

14 14

16 16

18 18

Results Results

58. 58.

::::J ::::J

en en ~ ~

0 0

!!? !!?

(J (J E E

~ ~

E E

V V

(/) (/)

Q) Q)

:::s :::s

......

(/) (/)

Q) Q) 0 0

...., ....,

<( <(

-c -c

:E :E

·-

"C "C

-e -e

hapter hapter

Figure Figure C Chapter V. Results and Discussion 129

5.3 Mixture Optimization

After model equations have been defined and validated a mixture optimization was conducted to obtain the desired combination of DBS, HPC, Glycerin and

Propylene Glycol that will beS: achieve physical property that is reasonably close to the soap benchmark, Johnson's Baby Clear Soap (detailed formulation in

Chapter 2 Table 14). This involves simultaneously satisfying all the requirements placed on the response (physical property) and input variables ( ingredient level) combined. Optimization uses the models from each of the individual response physical property and Design Expert Software performs optimization in two general ways: Numerical and Graphical Optimization.

To determine the best combination of ingredients to make up the cleansing bar matrix, an objective function, Desirability Index was used. The q represents the desirability for each of the response i. The value of q ranges from 0-1 (from least to the most desirable).

The simultaneous objective function, Desirability, is computed as,

Desirability Index= (d1 x di x .... dn)1'0 (Equation 5.3)

Where n is the number of responses being optimized Chapter V. Results and Discussion 130

Numerical Optimization was used to optimize the combination of goals. The goals may apply to either factors (ingredient levels) or responses (physical properties). The possible goals are: maximize, minimize, target, within range, none (for responses only) and set to an exact value (factors only). A minimum and a maximum level must be provided for each parameter included in the optimization.

Table 24 summarizes the numerical optimization goals, which are expressed as:

a) In-range, minimum and maximum for ingredient concentration, and

b) In-range, minimum and maximum for physical property data

The above ingredient levels and physical property limits were set based on the response data worksheet used to generate the model equations. Note that the

"importance" of a goal can be changed in relation to the other goals. The default is for all goals to be equally important at a setting of 3 pluses (+++ ). Foam volume being critical was designated a degree of importance of 5. Since the range of operable region allows for only a maximum of 440mL-foam volume, lower than Johnson's Baby Clear Soap, the goal is to be as close as possible to this maximum value. Recall that the DBS-solidified matrix uses a different solid- Chapter V. Results and Discussion 131

gellation technology to that of the soap benchmark, hence it is expected that some of its properties may significantly differ from the benchmark.

Table 24. Optimization criteria

VARIABLE GOAL BENCH- MIN MAX IMPOR- MARK (%) (%) TANCE (Clear (l=low to Soap) 5= high) DBS(%) Minimize 0.5 5.0 3

HPC(%) In Range 0 1.0 3

Propylene Maximize 0.4 50.0 3 Glycol(%) Glycerin (%) In Range 18.7 73.8 3

Penetration Minimize 15 77 279 3 (1/10 mm) Bar Wear(%) In range 57.6 2.2 58 3

Bar Mush(%) Minimize 6.7 2.5 50 3

S yneresis (%) Minimize 0.6 3.8 7.6 3

Foam Volume Maximize 503 210 440 5 (mL) Transparency In range 1 4.5 5.5 3 (Rank)

The above goals are combined into the overall Desirability Index. Figure 59 illustrates the Design Expert numerical optimization sheet in the Design Expert

Software. Chapter V. Results and Discussion 132

~ \\Jjpauborcdl\projecls\Asia Pacific Research\Oanny Lambino\MDE\nmtfina1J.d,c6 • Design·Expert 6.0.0 file Edi! View Display Options Des,;in Tools Help ...=0=1(ii;= ~1~=1--===1 =l= PI :d!J I _J Notes ror nm11n~3 ••· Design . .,.,, status DBS HPC PO G!.Y Qoa1 IHMi,Hrnlll .:] :- .J' Analysis (Penetrolton)'2 63 Bar wear i- ! Penetratlon(AnNyze: Lower Upper Ln(Bar Mush) l Ba, weor(Analyzec j Syneresis b1mjs· I 0 5 1 s ~ j Ser Mush(Anolyzed Foam Volume ~-- !- j Syneresis(Anolyzec Transparency Weights: I 1, : L Foam Volcme(Anoly Qpt1ons .. tmportance: ~ L. ! Transparency(Anal\ 1 0pt11T11Iet1on

Graphical - ~ Point Prediction

7~~I 0.50 5.00

DBS

Ready DIP

Figure 59. Numerical optimization criteria sheet

From the Design Experiment output, the best cleansing bar formula that meets all the above goals has a Desirability index of 0.63. While the ideal value of l was not achieved, the result is still acceptable given the requirement of satisfying all l O goals. Table 25 provides five numerical optimum solutions based on the above optimization criteria. Table 26 shows predicted versus actual response data for recommended optimum formulation number l. The formulation was made and responses were measured and compared versus predicted data. It can be inferred that solution number I bests fit the overall goal from actual response data.

lity lity

0.52 0.52

0.54 0.54

0.59 0.59

0.62 0.62

0.63 0.63

Desirabi Desirabi

\33 \33

Foam Foam

245.17 245.17

264.48 264.48

319.39 319.39

357.79 357.79

367.93 367.93

Volume Volume

is is

5.40 5.40

5.33 5.33

6.34 6.34

6.44 6.44 6.49 6.49

Syneres Syneres

2.73 2.73

Bar Bar 4.72 4.72

5.08 5.08

4.84 4.84

5.03 5.03

Mush Mush

Bar Bar

2.15 2.15

9.16 9.16

14.37 14.37

16.86 16.86

wear wear

16.73 16.73

65 65

143 143

112 112

122 122 118 118

ion ion

Penetrat Penetrat

GLY GLY

21.16 21.16

21.97 21.97

63.29 63.29

69.33 69.33

71.16 71.16

PG PG

8.06 8.06

2.33 2.33

0.39 0.39

50.00 50.00

49.72 49.72

0.99 0.99

0.29 0.29

0.00 0.00

0.01 0.01

HPC HPC

solutions solutions

Discussion Discussion

and and

2.84 2.84

2.45 2.45

3.36 3.36

3.05 3.05

3.15 3.15

DBS DBS

Optimal Optimal

Results Results

V. V.

25. 25.

5 5

4 4

3 3

1 1

2 2

No. No.

Chapter Chapter Table Table

134 134

Inferior Inferior

Acceptable Acceptable

Superior Superior

Inferior Inferior

ASSESSMENT ASSESSMENT

required required

510 510

Not Not

57.6 57.6

15 15

6.5 6.5

BENCHMARK BENCHMARK

VS VS

2.17 2.17

7.26 7.26

-4.83 -4.83

-7.27 -7.27

-1.54 -1.54

VARIATION VARIATION

% %

PREDICTED) PREDICTED)

(ACTUAL (ACTUAL

13.2 13.2

3.25 3.25

310 310

166 166

4.5 4.5

ACTUAL ACTUAL

data data

response response

13.0 13.0

3.1 3.1

179 179 289 289

4.6 4.6

PREDICTED PREDICTED

actual actual

(mL) (mL)

(mm) (mm)

versus versus

Discussion Discussion

and and

Volume Volume

Wear(%) Wear(%)

Mush(%) Mush(%)

Predicted Predicted

Results Results

Transparency Transparency

Foam Foam

Bar Bar

Penetration Penetration

V. V.

26. 26.

5. 5.

1. 1.

3. 3.

4. 4.

2. 2.

PROPERTY PROPERTY

Chapter Chapter Table Table Chapter V. Results and Discussion 135

Figure 60 provides a graphical solution plot. With multiple responses it is good to find regions where requirements simultaneously meet the critical properties, the

"sweet spot". By superimposing or overlaying critical response contours on a contour plot the best compromise is achieved and illustrated graphically.

Graphical optimization displays the area of feasible response values in the factor

(ingredient level) space. Note that regions that do not fit the optimization criteria are shaded gray. In the graph, any "window" that is not shaded gray satisfies the multiple constraints on the responses while the area that satisfies the constraints is shaded yellow. A flag of a predicted formulation is shown indicating the physical properties predicted by a particular combinations of DBS, Glycerin and Propylene

Glycol at a given concentration of HPC. The flag can be moved around the graph

(both inside or outside of the "acceptable" area of the graph) to show predictions for all responses at any location in space. C hapter V . Res 11/ts a n d D 1sc 11ssio 11 136

DESIGN - EXPERT Plot A : DBS Overlay Plot X1 =A : DBS X2 = D : GLY X3 = C : PG

• Design Points Actual Component B : HPC = 0 .22

Penetratio179 . 11 B a r we a r :1 3 . 4 3 8 4 Bar Mush :5 . 22222 Moisture ~ . 35883 Foam Vol01ttl .748 Transparel!l . 44342 X1 2 .00 X2 22 . 79 , e1 x3 49 .70 • 1Transoarenc "'-: 4 . 5

7 3 . 99 0 . 50 5 5 .28 D : GLY C : PG Overlay Plot

Figure 60. Optimal solution overlay plot Chapter V. Results and Discussion 137

5.4 Morphological Characterization

It was shown in Chapter 1 that DBS at varying concentrations forms different morphological structures, assembly size, aggregation behavior and orientation depending on the type of solvents used and presence of other polymers in the matrix. It was also shown that these morphological characteristics of DBS have profound effect on the physical properties of the system, particularly on the rheological behavior, strength, rigidity and in some cases opacity of the resultant matrix.

It is therefore expected that DBS will exhibit different morphological characteristics in the solvent-surfactant system under study by varying the solvent, DBS, HPC, and surfactant species and combinations, thereof. In this section, investigation was conducted to determine the type of DBS morphology formed at different concentrations of DBS, free water and HPC in the surfactant system and correlate these characteristics to the physical performance properties of the cleansing bar matrix. An understanding of morphological behaviour in these matrices will offer practical approaches in addressing physical performance gaps in the system. The characterization techniques used in studying the morphology of DBS in the system include

Atomic Force Microscopy ('\FM) for a high-resolution surface topography and Freeze-fracture Transmission Electron Microscopy (FF-TEM) for internal Chapter V. Results and Discussion 138

view of sub-micron structures in the matrix. Details of the equipment description, principles of use and operating procedure are presented in Chapter

5.4.1 Surface Topography of DBS-solidified matrix

Sections 5.1 to 5.3 illustrated how DBS significantly influence bar physical properties. It positively impacts on bar wear, mush formation and hardness and negatively affects foaming especially at higher concentrations. AFM provides an in-situ determination of the surface topography of the DBS solidied surfactant-solvent systems including DBS' physical orientation, formation and aggregation characteristics on the surface and as they relate to the physical performance properties of the matrix.

Most of these physical properties are surface phenomenon. Syneresis for example occurs at the interphase between the surface of the bar and the surrounding air, in which case the higher the moisture gradient, the more moisture is adsorbed on the surface. Moreover, the effect of free water content on DBS morphology is also critical since we found that increasing level in the formulation reduces syneresis with significant loss in both hardness and transparency. Other properties like bar wear and foaming are also a function of the susceptibility of the surface of the bar to mechanical abrasion and swelling, respectively. Chapter V. Results and Discussion 139

The DBS-solidified cleansing bar formulations used in the study were made following the process described in Chapter IV Section 4.4.5 and control samples for comparative evaluation were commercially available sodium soap and sodium-triethanolammonium soap which is Johnson's Baby Clear Soap used as benchmark product in the mixture design optimization study in Section

5.3.

Specimens were prepared by first cutting 0.5 mm thick x 30mm x 10mm surface area of the test sample. Each of the specimen was soaked with purified water for 12 hours and dried in 10.s°C oven for 15 minutes prior to AFM scan.

The specimen samples are saturated and then later dried to keep the surface intact and free of moisture while scanning. The room where AFM was conducted is also under controlled humidity and temperature.

The formulations in Table 27 were subjected to AFM to determine effect of

DBS concentration and presence of HPC and free moisture on the morphology of DBS in the system vis-a-vis sodium soap and sodium-triethanolammonium soap. Chapter V. Results and Discussion 140

Table 27. Formulations subjected to AFM

Sample Number DBS HPC Free Moisture

1* .... 1.00% 0.75% 0

2'" 1.00% 0.00% 0

3-t- 1.00% 0.75% 15.00%

4 Sodium soap

5 Triethanolamine-Sodium Soap

*DBS solidified glycerine-propylene glycol surfactant matrix per formula in Table 22. +non-DBS and HPC components concentrations are constant per formula in Table 22.

Figure 61 shows a three-dimensional topographic image of Sample 1 in a scan area of 2 x 2 µm2 . The image shows distinct formation of long nanofibrils and fibrillar bundles of DBS on the surface of the bar matrix. The fibers are twisted and interconnected in a three-dimensional percolation network.

Section analysis in Figure 62 reveal typical fiber width of around 40nm. (The protruding fibers' diameter is denoted by the distance between the two inverted red triangles. A cross section line is drawn across the image and the vertical profile along the line is displayed. Each pair of cursors in the image will give horizontal, vertical and angular measurements of the point or points of interest. ) Chapter V. Results and Discussion 141

The role of DBS in tre structural formation of the cleansing bar matrix is quite evident in this topographical image. It can also be inferred that the crossing, twisting and multidirectional orientation of the fibers provide rigidity to the solid gel network.

42 42

1. 1.

Sample Sample

of of

image image

AFM AFM

topographic topographic

dimensional dimensional

D1scusswn D1scusswn

and and

s s

Three Three

61. 61.

. .

Figure Figure Chapter Chapter

3 3

nM nM

OM OM

nM nM

OM OM

nM nM

OM OM

deg deg

Hz Hz

108.32 108.32

1,828 1,828

1.828 1.828

2 2

0,095 0,095

DC DC

0.447 0.447

0.769 0.769

39,063 39,063

DC DC

0 0

0.0002 0.0002

1.274 1.274

0,869 0,869

39.063 39.063

39,287 39,287

) )

Cnt Cnt

aMp aMp

triangles. triangles.

le le

Radius Radius

Rz Rz

RMa>< RMa><

Ra(lc

RHS RHS

SigMa SigMa

L L

freq freq

period period

RHS RHS

distance distance

distance(L) distance(L)

inverted inverted

distance distance

using using

Angle Angle Off Off

Uert Uert

Horiz Horiz

Spectral Spectral

Surface Surface

Angle Angle

Uert Uert

Horiz Horiz

Angle Angle

Uert Uert

Horiz Horiz

Surface Surface

I I

Clear Clear

measured measured

is is

Offset: Offset:

Analysis Analysis

Hin Hin

Offset Offset

width width

Off Off

Fiber Fiber

Line Line

1. 1.

line: line:

Section Section

I I

SpectruM SpectruM

1.50 1.50

Cen Cen

Center Center

Sample Sample

of of

DC DC

'f 'f

ZooM ZooM

I I

JJM JJM

1:1 1:1

1.00 1.00

Analysis Analysis

on on

SpectruM SpectruM

scuss

ZooM: ZooM:

d d

Section Section

I I

s s

0.50 0.50

ull

Harker Harker

AFM AFM

fi>

. .

62. 62.

er er

I I

OM OM

0 0

~ ~

_ _

01091354.001 01091354.001

Cursor Cursor

I I

Cursor: Cursor:

Figure Figure

0 0

It) It)

It) It) Chap Chapter V. Results and Discussion 144

5.4.2 Role of HPC in the DBS morphology in the matrix

Figure 63 is a three-dimensional topographic image of DBS-solidified matrix without HPC (Sample 2). In the absence of HPC, DBS appears to have less defined fibrillar structures and with somewhat flat fiber cross-sections as depicted by vertical distance of only 0.19nm in the Section Analysis in Figure

64. The cross section of the fiber (32 nm) is shorter by about 10nm than

Sample lmatrix containing both DBS and HPC.

We were unable to isolate HPC morphology since the specimen sample without DBS is too soft at 25'C to be able to do an acceptable comparative

AFM scan.

The role of HPC as a gelling synergist to DBS's structural formation while not fully understood is manifested in the difference in DBS's morphological structure between sample matrices with and without HPC. HPC's interactive effect on DBS morphology appears to contribute to cross-linking of fiber network and formation of thicker and more rounded fiber cross-sections. This translated to improved wear rate and hardness of the matrix.

45 45

. .

Sample Sample

of of

image image

AFM AFM

topographic topographic

dimensional dimensional

D1scusswn D1scusswn

and and

s s

Three Three

Resu

63. 63.

. .

Figure Figure Chapter Chapter

6 6

nM nM

nM nM deg deg

Hz Hz

0.145 0.145

34.084 34.084

2 2

1.598 1.598

3.837 3.837 DC DC

3.837 3.837

0.982 0.982

31,250 31,250

DC DC

0 0 0.00005 0.00005

0.348 0.348

0.190 0.190

31.250 31.250

32.404 32.404

Cnt Cnt

aMp aMp

triangles. triangles.

le le

Radius Radius

Rz Rz

RMa>< RMa><

SigMa SigMa

RHS RHS

L L

RaClc) RaClc)

freq freq

RHS RHS

period period

distance distance

distanceCL) distanceCL)

inverted inverted

distance distance

using using

Off Off

Angle Angle

Uert Uert

Spectral Spectral Horiz Horiz

Spectral Spectral Angle Angle

Uert Uert Spectral Spectral

Horiz Horiz

Angle Angle

Surface Surface

Uert Uert

Horiz Horiz

Surface Surface

I I

Clear Clear

measured measured

is is

Offset: Offset:

Analysis Analysis

Hin Hin

Offset Offset

width width

Off Off

Fiber Fiber

Line Line

2. 2.

line: line:

Section Section

I I

SpectruM SpectruM

1.50 1.50

Cen Cen

Center Center

Sample Sample

of of

DC DC

'f 'f

2ooM 2ooM

sis sis

I I

J.JM J.JM

1:1 1:1

1.00 1.00

Anal

ion ion

SpectruM SpectruM

ZooM: ZooM:

Section Section

I I

and and

s s

0.50 0.50

001 001

Harker Harker

fixed fixed AFM AFM

. .

64. 64.

I I

nM nM

0 0

_ _

01111520. 01111520.

Cursor Cursor

I I

Cursor: Cursor:

Figure Figure

0 0 o

0 0

o 0 0

- Chapter Chapter Chapter V. Results and Discussion 147

5.4.3 Effect of free water on DBS morphology in the matrix

The effect of addition of 15% free water on the morphology of DBS in the matrix was also studied. Sample 3 was prepared following the formulation in

Table 22 and the procedure outlined in Chapter IV Section 4.4.5. 15g of purified water was added into 85g of molten matrix at 75-80°C at 200rpm and mixed for 2 minutes. The resultant mixture is allowed to cool and harden inside a dessicator overnight to prevent syneresis prior to specimen preparation.

Results indicate that adding 15% free water alters the DBS structure in the matrix. This is manifested in the AFM image of the bar surface in Figures 65 and 66 indicating ribbon-like fibers with no cross-linking compared to more round and highly cross-linked fibers in the original matrix. Section Analysis also indicate thinner fiber diameter of around 24nm, which is about half the diameter of DBS in the original matrix without free water.

The absence of DBS cross-linking and thinner fiber cross section weakens the matrix structure and supports earlier findings that addition of free water significantly reduce bar hardness.

8 8

s. s.

tri

erted erted

using using

d d

asur

is is

width width

Fiber Fiber

3. 3.

Sample Sample

of of

Analysis Analysis

Discussion Discussion

Section Section

and and

s s

AFM AFM

65. 65.

V. V.

Figure Figure Chapter Chapter Chapter V . Resu lls and Discussion 14 9

Digital InstruMents NanoScope Scan size 2.000 lJM Scan rate 0.2999 Hz NuMber of saMples 256 IMage Data Height Data scale 250.0 nM

[g] view angle -°(1)'- light angle , I '

[g]

Y I--< 0.5 - - ),...( ',-

1.0

0 X 0.500 lJM/div deg lJM Z 250.000 nM/div 01091312.001

Figure 66. Three-dimensional topographic AFM image of Sample 3. Chapter V Results and Discussion 150

5.4.4 Morphology of soap bar matrices

The surface topography of soap bars was also studied in comparison to the

DBS-solidified matrices. AFM scan of Johnson' s Baby clear soap and commercial opaque soap bars are shown in Figure 67a and 67b. The images did not reveal fibrillar network structures but instead a more organized sheet-

1ike crystalline surface for both matri:es. The white particles in the opaque soap matrix measuring around 50um are aggregates of titanium dioxide and disodium EDTA particles, which were incorporated as powder in the soap matrix. Titanium dioxide is used as opacifier while disodium EDTA as chelating agent.

1eo.o deg

30,0 deg

D, 11 Ha I I ns t n;-n ts Na-$0011 Sc.an size 5 . 000 u• Sc. ...., rate 1 . 001 lb. Nu.. 1,er or s.~ ..Ple5 256 •-!lie o.. t.. Phase D•t• s gal • 60. 00 dew ,...

01111soa.001

Figure 67a. Sµm x Sµm AFM image of clear soap Chapter V Resu/1.s and Discussion I 5 I

Cl ear Execute Un.do

125.0 n1111

Oi9ital lnstru..ent~ HanoSco.,e Soan s in 2, 000 UOII Scan rate 0.6013 Hz ttu..1,er of s.a..pl es 256 ....ii" 0 t H 1r,ht Data scale 125.0 ON

/,IOII

01091343. 001

Figure 67b. 5µm x 5µm AFM image of opaque soap. Chapter V. Results and Discussion 152

5.4.5 Freeze-fracture Transmission Microscopy

Freeze-fracture Transmission Electron Microscopy up to 120,000x magnification was used to determine the size, shape and arrangement of structures and their relationships inside the matrix. Figures 68 to 72 provide electron micrographs of the different formula matrices with various structures referenced in Table 28.

Table 28. Internal structure comparison

Sample DBS HPC Structure Size

1 1% 0.75% Crystalline, mostly 6µ.m rectangular

2 0 0.75% Vesicle-like structure, 0.05to 0.19µm some hexagonal mean of 0.091lm

3 1% 00/o Crystalline, some lµm hexagonal

Clear Random, non-organizes Not applicable Soap structure

Opaque Organized matrix, sheet- Not applicable Soap like lattice structure Chapter V. Results and Discussion 153

5.4.5.1 DBS and HPC in surfactant matrices

Figures 68-70 shows rectangular and hexagonal structures found in samples 1 to 3 with size ranging from 0.05 to 6,lm. These structures could be surfactant micellar aggregates and their shapes (hexagonal, vesicle-like and rectangular) are possibly influenced by the presence and absence of DBS and HPC in the matrix. Unlike in the AFM topographic images, there were no fibrillar structures found. Chapter V Results and Discussion 154

Figure 68. Freeze-fracture TEM images of DBS + HPC Solid gel matrix Chapter V Resulls and Discussion 155

Figure 69. Freeze-fracture TEM images of DBS only Solid gel matrix Chapter V Results and Discussion 156

Figure 70. Freeze-fracture TEM images of HPC only gel matrix Chapter V. Results and Discussion 157

5.4.5.1 Clear and Opaque soap structures

Figure 71 shows clear soap structures which appears more random, unorganized and irregular in shape. Figure 72 shows opaque soap structures that are sheet-like lattices that resembles more of the AFM images. Chapter V. Results and Discussion 158

Figure 71. Freeze-fracture TEM images of JB Clear Soap solid matrix Chapter . Results and Discussion 159

,I K I! l fl Ofldt!ll <' l O.IUIII

Figure 72. Freeze -fracture TEM images of Opaque soap solid matrix Chapter VI. Conclusions 160

VI CONCLUSIONS

1. MOE was a useful tool in optimising the DBS-solidified cleansing bar properties given the limitations and mixture constraints inherent in the technology. The resultant optimised matrices have better bar wear rate and bar mush with comparable transparency to commercially available transparent soap, Johnson' s Baby Clear Soap.

2. The cleansing bar matrix was shown to have acceptable hardness and level of foaming.

3. The maJor disadvantage is the matrix' susceptibility to syneresis when exposed to high humidity due to the presence of high concentrations of propylene glycol and glycerin in the formula.

4. It was found that addition of free water from 5 to 15% reduces syneresis but also reduces rigidity and clarity of the matrix.

5. AFM was a useful tool in providing two-dimensional and three-dimensional topographic images of the matrix fiber geometry, width and assembly. It showed distinct formation of long nanofibrils and fibrillar bundles of DBS with each fiber cross-section measuring about 40nm. The twisting, Chapter VI. Conclusions 161

interconnection and multidirectional percolation network of DBS fibers provided rigidity to the matrix.

6. Introducing free water into the system results to a remarkable change in

DBS morphology with thinner fiber cross-sections and absence of crosslinking, consistent with the loss of structure of the matrix as evidenced by reduction in bar hardness and transparency.

7. Freeze-fracture Transmission Electron Microscopy was found useful in providing internal micellar aggregate structures of surfactants in the matrix.

However, unlike in the AFM topographic images, there were no fibrillar structures found. Chapter VI. Recommendations for Further Work 162

VII RECOMMENDATIONS FOR FURTHER WORK

From the findings of this thesis, the following are recommended future work:

1. Make surfactants types, concentrations and combinations variable in the mixture design of experiment. This will expand opportunities to improve foaming by incorporating high foaming capacity surfactants and improve bar rigidity without compromising other physical performance properties by providing structural support using surfactants in solid form.

2. Investigate combining soap solid matrices with the DBS-solidified matrix and determine effect on the morphological structure of DBS and the resultant physical performance properties of the system.

3. Investigate other technical approaches to address the syneresis in the matrix.

This may include a) Use less hygroscopic solvents than glycerin and propylene glycol like their corresponding ether derivatives and b) Dilution effect with non-polar solvents, silicone oils, or surfactants, inorganic powders with large surface areas and other polymers. Chapter VI. Recommendations for Further Work 163

4. Conduct NMR spectroscopy for the bar matrix for identification of the H bonded structures (qualitative and quantitative). Chapter VII. List of References 164

VII LIST OF REFERENCES

1. Shepard et al. Self-Organization and Polyolefin Nucleation Efficacy of 1,3:2,4 Di-p-Methyl Dibenzylidene Sorbitol, J. Polym. Sci. B: Polym. Phys., 35, 2617 (1997)

2. Yamasaki et al. The Polar Effects of Solvent on DBS Gel. Bull. Chem. Soc. Jpn, Vol. 68, No. 1. (1995)

3. Lambino, D., Clear Surfactant-based Cleansing Bar Base Development, Johnson & Johnson Internal Report (2000)

4. Roquette Disorbene Le Technical Brochure Roquette Freres France (1996)

5. The American Heritage® Dictionary of the English Language: Fourth Edition. Houghton Mifflin Company (2000)

6. Jungermann, E.,Clear Antiperspirant Stick Technology: A Review; Cosmetic & Toiletries, Vol 110, No. 2 (1995)

7. Fondots, D., Cosmetics and Toiletries Manufacture Worldwide, publ by Simon Bond and Martin Caine, Ashton Publishing Group, England, ISBN 0 9519830 (1993)

8. Henderson, C. Ed, Cult of Personality, Soap Perfumery and Cosmetics Magazine Vol 74, No 7 (2001)

9. Shepard, T.; Delsorbo, C.; Louth, R.; Walborn, J.; Norman, D.; Harvey, N.; Spontak, R.; Self-Organization and Polyolefin Nucleation Efficacy of 1,3:2,4 Di-p-Methylbenzylidene Sorbitol, Journal of Polym. Sci; Part B: Polymer Physics, Vol. 35, 2617-2628 (1997)

10. Uchiyama H., Process for Preparing Dibenzylidene Sorbitol and Composition Containing the Same. US Patent 4,267,110 ( 1981)

l l. Yamasaki et al. The Polar Effects of Solvent on DBS Gel. Bull. Chem. Soc. Jpn, Vol. 68, No. 1 (1995) Chapter Vil List ofReferences 165

12. Roquette Disorbene Le Material Specifications. Roquette Freres France (2001)

13. Rhoel E., Tan H., Solid Antiperspirant Composition and Process for its Preparation. US Patent 4,154,816 (1979)

14. Kobayashi T., Hasegawa H., Hashimoto T., Hihon Reoroji Gakkaishi 17, 155 (1989)

15. Mitra D., Misra A., J. Appl. Polym. Sci 36, 387 ( 1988)

16. Mitra, D. and Misra, A. Polymer 1988, 29 (1990)

17. Ilzhoefer, J. and Spontak, R. Effect ofPolymer Composition on the Morphology ofSelf-Assembled Dibenzylidene Sorbitol. Langmuir, Vol. 11, No. 9. (1995)

18. Ilzhoefer, J. et al Evidence ofHierarchical Order in an Amphiphilic Graft Terpolymer Gel. J Phys. Chem. Vol 99, No. 32 12069 (1995)

19. Cuvelier G.; Launay, B. Makromol. Chem. Macromol. Symp. 40, 23 (1990)

20. Kilpatrick, P.; Khan, S.; Tayal, A.; Blackbum, J. Structure and Flow in Surfactant Solutions; Herbs, C.; Prud'homme, R. Eds; ACS Symp. Ser. 578; American Chemical Society: Washington, DC, 229 ( 1994)

21. Mitra, D. and Misra, A. Polymer, 29, 1990 (1988)

22. Dolgopolsky, A.; Silberman, A.; Kenig, S.; Polym. Adv. Technol., 6, 653 (1995)

23. Thiery, A. et al, Progr. Colloid Polym. Sci, 87, 28 (1992)

24. Kobayashi, T. et. a.I, Hihon Reoroji Gakkaishi 17, 155 (1990)

25. Kobayashi, T. et. al, Hihon ReorojiGakkaishi 18, 155 (1990)

26. Kim, C.; Kim, C.; Kim, S. Polym. Eng. Sci., 33, 1455 (1993)

27. Ssterzynski, T.; Lambla, M.; Crozier, H.; Thomas, M. Adv. Polym. Technol., 13, 25 (1994) Chapter VII. List ofReferences 166

28. Smith, T.; Asilamani, D.; Bui, L.; Khanna, Y.; Bray, R.; Hammond, W.; Curran, S.; Belles, J.; Bindercastelli, S. Macromolecules, 27, 3147 (1994)

29. Fujiyama, M.; Wakino, T. J. Appl. Polym. Sci., 42, 2739 (1991)

30. Fujiyama, M.; Wakino, T. J. Appl. Polym. Sci., 42, 2749 (1991)

31. Kim, C.; Kim, C.; Kim, S. Y. Polym. Eng. Sci, 31, 1009 (1991)

32. D. Mitra and A. Misra, J. Appl. Polym. Sci., 36, 387 (1988)

33. Fuchs, K.; Fahrlander, M.; Friedrich, Chr.;. Cantow H. Rheological Investigations ofSelf-organizing Sorbitol Networks in Amorphous Polymer Matrices. Poster Presentation on Discussion Meeting on Multi-Level Ordering by Competing Short and Long Range Interactions in Polymers, Weingarten (2000)

34. Albanese, J., Schamper, T., Clear Antiperspirant Stick with Dibenzylidene Sorbitol and Guar and Process ofMaking Same. US Patent 5,895,644 (1999)

35. Kauffman, M., Gregorie, N., Quemin, E., Cosmetic Composition in the Form ofa Solid Gel. (1994)

36. McCall, P., Antiperspirant and Deodorant Stick. US Patent 4,743,444 (1988)

37. Roquette Disorbene Le Formulary (1996)

38. Lambino, D., Gelatin for Preparing Solid Surfactant System, Johnson & Johnson Internal Report (2001)

39. Roehl E. L., Solid Antiperspirant Composition and Process for its Preparation. US Patent 4,346,079 (1982)

40. T Schamper. M. Jablon., MH Randhawa, A Senatore and JO Warren, Acid Stable Dibenzylidene Sorbitol Gelled Clear Antiperspirant Formulations, J. Soc. Cosmet. Chem. 37 225-231 (1986)

41. S. Gupta, Soap Chemistry, Chemical and Physical Properties & Raw Materials, American Oil Chemist's Society ( 1990) Chapter VII. List ofReferences 167

42. A. Kassem, A. Mattha, and G. K. El-Khatib Influence ofSome Humectants on the physical Characteristics ofSolidified Sodium Stearate-based Sticks (1982)

43. Milwidsky B., Soap and Detergent Technology, Household & Personal Products Industry (1980)

44. Laden, K. Ed., Antiperspirants and Deodorants (1999)

45. Leiner Davis Gelatin, Gelatin for General Food Application (1999)

46. Cosmetics & Toiletries Formulary Vol. 114, No. 12 (1999)

47. Roquette Disorbene LC Material Safety Data Sheet (1999)

48. Brewester, D.A., Dobkowski B. J., John, F., Orofino, S. A., Underarm Compositions. US Patent 5,922,308 ( 1999)

49. Johnson & Johnson internal document (1990)

50. Mazoni LB Processing Plants and Equipment for the Soap and Glycerin Industries. (2001)

51. Spitz L., Ed., Soap Technology for the 1990 's, American Oil Chemists' Society (1990)

52. Lambino, D. Clear Colorless Soap Bar with Superior Mildness, Lathering and Disco/oration Resistance, US Patent 5,728,663 ( 1998)

53. Orark, J. R., Low pH Detergent Bar. US Patent 5,922,308 (1979)

54. Johnson, D., Alternatives to Glycerine in Cosmetics (1991)

55. Jungermann E. and Sonntag, N., Editors, Glycerine, A Key Cosmetic Ingredient ( 1991)

56. Porter M., Handbook of Surfactants td Ed. (1994)

57. ACD Lab Chemsketch Software (2002)

58. Hunting, A., Encyclopedia of Shampoo Ingredients (1985)

59. Aqualon Klucel Hydroxypropyl Cellulose Technical Brochure ( 1999) Chapter VII. List ofReferences 168

60. Dow Chemical Technical Brochure of Versene NA (2000)

61. Dow Chemical Material Specifications of Veresene NA (2000)

62. Lieberman, et al. Pharmaceutical Dosage Forms: Disperse Systems Volume 2, Jd Ed. Marcel Dekker, Inc. (1996)

63. Lambino, D. Test Method for Bar Penentration_ Johnson & Johnson (1999)

64. Lambino,D. Test Method/or Foam Volume. Johnson & Johnson (1999)

65. Lambino, D. Test Method for Soap Mush. Johnson & Johnson (1999)

66. Lambino, D. Test Method/or Bar Wear. Johnson & Johnson (1999)

67. Manual of Operation for Humidity Chamber. Johnson & Johnson (1999)

68. Lambino, D. Test Method/or Syneresis_ Johnson & Johnson (1999)

69. Wills H. H., Introduction to Atomic Force Microscopy, Physics Laboratory, Unversity of Bristol (1999)

70. Scanning Probe Microscopy Training Notebook, Atomic Force Microscopy. Digital Instruments (1999)

71. Stat-Ease Design of Experiments Training Manual 2 (2000)

72. Stat-Ease Design of Experiments Guide Book 2 (2000)

73. Design Expert 6 Software (2002) APPENDIX 1-10

Material Specifications for:

1. Propylene Glycol

2. Glycerin

3. Sodium Laureth Sulfate

4. Sodium Laureth-13 Carboxylate

5. PEG 80 Sorbitan Laurate

6. Cocamidopropyl Betaine

7. Sodium Lauroamphoacetate

8. Hydroxypropyl cellulose

9. Disodium EDTA

10.Dibenzylidene Sorbitol USPID PROPYLENE GLYCOL

Data Sheet Product Information

Dow ~ ~ USP/EP jUnlted States A9macopela. EUl'0PW1 Pharmacopoeia) Is a ~ purity grade of Monopropytane Glycol for usage in plamaceutlcals, C09ffllllica, fragrances and flav0ln and a Y8rieCy of olher applcallons. The dear, eoloul1ess, practicely odourless, slighlly lliscous and twoacoPIC liquid with low V8J)0U' ~ is pioduced in compllance with Good Manufacturing Practice (GMP) guidelines. In adcttion to meeting USP and EP specifications, l'l'opylene Glycol USP/EP con'*'8 with the Japanese Pharmacopoeia and other pharmac8uticel, cosmetic and food regulations in global mar kats where It is sold.

Chemical Name 1 2- Formula ,_.__.., ,..._,,~-Qi20H; C3H802 Molec;ularWAlahl 76.10 CASNumber 57-55-6 EINECSNum:>er 200-338-0 >99.8'11,bY-.t water <0.2'!1.bvweait -Bolllna Point, 101.3 kPa 187.4-C DildlatiorlAannol, 101.3kPa 1B6-189"C Vapour Pre&aln, 20-C 0.011 kPa (0.08 mm l-lgl 25-C 0.017 kPa (0.13 mm Hal Ff9ezinll Point - Pol,Paint < -57"C Speciftc Gravity 20l20°C 1.038 2514"0 1.033 60/'4°0 1.007 Refrective Index n20/D, 20°C 1.4310-1.4330 Vlsco91ty. 25°C 48.8 oenUpoise (mPa.s) 80"C 8.4 oanllmiM (mPa.8) ~Heat,25-C 2.51 J/a·K Surface Tension, 25°C 36mNlm Flash Point,.. Pensky-Marl918 closed """ 104°C T1.. • 371°C Thermal • 25°C 0.2081 W/m·K 8ectrical ,...,,..,.,_ ... , 25°C ' 10mlaoSlm Heat of formation -422 kJ/mol (-101 KaiVn-mnll Heat of Vaporisallon. 25°C 67.0kJ/mcl DOW Glycerine 99.5¾ USP .....Page I of2

DOW Glycerine 99.59/e USP/EP

DOW Glycerine 99.5% USP/EP shares a similarly high level of the pwity, quality and consistency ofOPTIM• Glycerine 99.7% USP/EP. It offers the same superior sensory qualities that won't alter the taste or smell. Manufactured from consistent and unifonn synthetic raw materials free from animal fats and vegetable oils. Available in Kosher ~-This product is not available in North America.

Physical Properties

glc:c3, 25°C 1.25802 lb/gal, 25•c JO.SO Dielectric constant, 20°c Not Applicable

Empirical formula C3H10 3 Flash point, PMCC (Pensky Martens Closed Cup) I 95.S°C (384°F) Freezing point 17°C (62.6°F) Heat capacity, 2S°C, cal/gm, 25°C 0.62 Heat of fannation, kc:al/mo). 25°C 159.1 Heat of fusion, c:al/gm 47.S Heat ohaporil.illion, cal/mol, SS°C 21,060 Molecular weight 92.09g/mol Odor Odorless Reuactive index. 20°C 1.47399 Solubility, 25°C Benzene Immiscible Chloroform Immiscible

https://www.dow.com/g)ycerine/products/dowglyc99.hbn 7/08/2002 DOW Glycerine 99.5% USP Page 2 of2

Ethyl alcohol Miscible Ethyl ether Immiscible n-Heptane Immiscible lsopropanol Miscible Water Miscible Specific gravity, 2S/2S°C 1.26201 Surface tension, Dynes/cm, 20°C 63.0 Taste Sweet

Vapor pressure, mm Hg<21 SO°C 0.0025 100°C 0.19S Viscosity, Cp, mPa s, 20°C 1410

(I) TI,e.., IR lypical valua only, 1111d..., DOI ID be reprdod - Siles -~;~... advised lo ooafinn fur their operations. (2) I mmHg-0.IJJHPa

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• Ttldenmlc of The Dow Cllanical Com.,..y

COpyngMOToe Dow Chemical Company (1995-2002). Al Rlglm Res8Mld.

Plivac:y Slalement I lotwnet Diedaimer

https://www.dow.com/g)ycerine/products/dowglyc99.hun 7/08/2002 HUNTSMAN SODIUM ALKYL ETHOXY SULPHATE

EMPICOL ESC 70

EMPICOL • ESC 70 is ., aqu_. 10Utia11 af a IDilllry grade of sodium laur)'I ell-, ( JEO ) sulplale based on a nanuw cut pnanwy nan! alcohol.

Characteristics EMl'ICOI..ESCJe

PIIWslcal Typcal propetti.s :

~ a1 25•c Free lowing opeque lquid Colour Practically colourtass Density at 20·c 1.10glan' Slit point a·c Villcollily@ 25•c 5000 m.Pa.s. csi-rate or 108-')

Chemical Specification : Ac11w: ma118r (MMW 428) 70.0 :t 1.0% URIUlphabld mallllr 3.5%max. Sodium sulphate 1.5%max. Sodium chloride 0.3%max. pH (2% !IOlullon) 6.0:t1.0 Anal)lfi::al melhod1J .. ..,.....,, an l8qUNt

Applications This product is a vanalle toiletry ,_ matarlal which combines liplmum perfonnance wilh ecellnt foamW1i1 charactari&tica. It Is used in !he bmulalion ol high qually :

Har shanpoos Foambalhs S'-produds Liquid aoaps 0-n:t lollons The wico&ily ol ._ dllMld bmulallona can be adjusted by Iha addition of inorganic Salls or surfactants such as EMPIGEN 08, EMPtGEN BSIP, EMPLAN coe. etc. · ½%½½½%½%½%½%½½½%½%½½½½½% The mldneN or a product bmulalad wilh EMPICOL ESC 70 may be mprOVlld by lhe inclusiDn or ~ l1tl EMPIGEN CDR -.is, or a cocamido ~ belaine. lhe EMPIGEN BS sar1as. ASIA PACIFIC Raw Material Specification

Company: JOHNSON & JOHNSON

Naae: SODIUM LAURIETH-llCARBOXYLATE

Doc•meat Code: RM-SIOOOI_..

I. PROPERTIES AND REQUIREMENTS

Origin: Svnthetic source and oontains no animal derived materials. TEST PllOPERTIES REQUIREMENTS TEST FREOUENCY MEllfODS • Appeamce Clear to slightly hazy, gel-like liquid lice from TM72S2 foreilm matter contamination. • Colorat25 Colorless to slightly yellow; shall be comparable to TM72S2 degreesC a reference standard • Odor Shall be comoarable to a reference standard TM72S3 •• lnfrared The in&ared spectrum of the sample shall exhibit TM 7144or identification absorption bands of the same pattern and placement Applicable as those exhibited by the standard, with no validated IR test extraneous bands ...... t. method •• Microbial Shall contain no detectable harmful TM7804 Content microorganism.s. Shall contain not more than I 0 microor2anisms ner gram of product. R1 pH at 10% 7.8 +/-0.8 TM7130 solution (at rime of manufacture) R1 Water Content 29-/o-33% MTM0l9or applicable validated Karl Fischer TM SC Solids Content/ · 67"/4-71% (at I hour; at 120 degrees C) Supplier Certified OYen Solids SC Sodium Chloride 2.0-4.0% Supplier Certified Content

1 Note: Any unusual condition not defined herein or any unusual frequency of defects will not be assumed to be acceptable but shall be reviewed critically by JOHNSON &. JOHNSON Quality & Technical Assurance for acceptability.

Legend: • ••

R R2 SC ace ifications

Issue Date: May 06, 2002 Page2 of3

1·. HUNTSNIAN

TERMUL4280

Document ID: SUR99n454

Revision No: 0

DESCRIPTION Solution of PEG 80 Solt>itan L.aurale

SPECIFICATION Add value, mgKOH/g 3.0max Hydroxyl value, mgKOH/g 20-35 Saponlllcatlon value, mgKOH/g 8-18 Water, %w/W 28.0-30.0 Colour, Gardner 7max 1,4-dloxane, ppm 10max Hydrogen peroxide, ppm 150max

TYPICAL·PROPERTIES Appearance @ 25•c Clear amber liquid Speclllc gravity @ 25•c 1.1 VISCOSly, cP @ 25"C 1000 Flash paint, •c >149 Firepom. •c >149 HLB 19.l

SOLUS/LITY TERMUL 4280 is soluble in water, ethanol, isopropanol and propylene glycol. It is Insoluble in mineral oh, Wllgelable ols and glycetin.

Produd Dala ShNfs.,. u,d*dfrwquently. ,,,,,_ _,,.., jllOII ,_ acutrMtcopy

Page 1 of 1 -

PT. GOLDSCHMIDT SUMI ASIB Joint Venture ofTh. Goldschmidt AG. Germany and PT. Sumi Asih, Indonesia Jl Ccmpaka - Jatimulya (Jl Raya Jakarta Bckasi Km. 38) Tambun- 17SIO, Bck.asi Timur, INDONESIA Tclcphonc:62-21-1828322 Fax: 62-21-8128321

c ....aer

Prodlld ..._ : T.- ..._ L 7

ProdactNo : 200225 Do No : DOF.llOOl/188

Testao. Unit Spee. Results

NaCl DGF-H-m 9-EA.44..01 % 4.5-5.5 4.9

Water DGF-C-W lla-EA.14.01 % 63-67 64.9

pev.a- DGF-B-m l-EA.86.18 4.5 - 5.5 5.0

Spec.gnvily at~ C DG.F~-IV 2-EA.19.04 1.04-US tj ••• 1.05 Actiwlaatter EA.45.04 % 29-32 3U

Celoa(acc. ta Ganlaer) EA.08.06 2 mH 0.2

CERTFICATE VERIFIED

Dr. Sari K••-waty Qm&lyMuacer PI'. GoW..aidt S•mi Asill HUNTSMAN ALKYL IMIDAZOLINE BETAINE

EMPIGEN CDL 30 / J

EMPIGEN.COL 30/J ii Maqu-,.IOMtion of sodium~.

Characteristics EIIPIGEN COL 3a I J

.....Typlcalprope,tills:

Appaa,ance al 25'C Coblr

_Chemlc:al ~: Sodium chloride 11.0 i: 1.0'II, pH (10'11, solulilln) 10.0t0.5 M~cantn,I No~culaniaa Solds 50.0t2.()'II, Diamide 0.45'11.max. Symmeln(:al dlanide 0.01'11. max. ~-819...... ,..ont9qfJN/ Applications EMPIGEN COL 30 / J is of particular interal tar incoll)Ollltio,, inlo low lnlancy formulalioml. Examples of th--;

• beby lhampooe and balh - plOduds • childNn's shampoos and bait, Clift pcodudS • mid lanly lh.,,Jll)09 811d ball, - products. Other auggllllad u- tar EMPIGEN CDL 30 / J .. in lquid hand soepe and houeehold and i'ldusbial c1ea1q applcalions. Ila formulation llerl9II& - : - Mldn-lD the llkrl and.,_ - EJClremelygood cald ..properlles • &lellantfaarmg p!llpeltiea, and good NII llllbatyin the~ of soap • Good campatllilywlh anionic, nottionic and celionic au.-r- aclMI aganlll Aqualon I Personal Care I Product Data 4175 Page 1 of 3

MEIICULIES

Product Data NUMBER.4176 (Supersedes 479-5)

KLUCEL.. Hydroxypropylcellulose Summary ol Properties and U...

Description KLUCELe hydroxypropylceluloa (HPC) is a nonmnic water-soluble cellulose ether with a versatile combination of pl'Operties. It combines organic solvent solubility, lharmoplasticity, and SUfface activity wilh the thickening and slabiiz:ing properties of other water-soluble cellulose polymers.

Outstanding Charactarlstics Klucel is soluble in many polar organic solvents and in water below 3a•c. but is insOluble in water above 45• C. Klucel is highly surfaca.ac:tive, with low suiface and lntetfacial tensions of solutions. H has a wide range of compatibility with latexes and with synthetic and natural colloids. Klucel Is available in a wida range of vilCOSities with measurements repo,ted at varying concentrations in both water and 283 ethanol. It is lhennoplastic and can be injection molded and extruded. In films and coatings, Klucel is heat-sealable. extremely flexible without plasticizers. and nontacky at 1191 humidity.

Uses Klucel is versatile: it is used In a wide variety of applications, including food, cosmetics, phannaceuticals, coatings, adhesives, extrusions. and moldings. paper. paint removers, encapsulations, inks, and many other appflc:atlons requiring a film-former, thickaner. stablizer, suspending agent. film barrier, thermoplastic, or protective colloid.

Grades and Types Klucel HPC is produced in standard and premium grades. Tha standard grades - for Industrial iae; the premium grades are for foods, pharmac;euticals, and cosmetics, and - designated with al least one •p after the vilcosity type. All viscouy types - avalable in each grade. Solution viscosities of the various types are shown in Table I. Typical properties of the polymer and Its solutlona are given In Table II.

Talllel Vlacosily(a) of Various Solullon r,.,.., cps

Collc:anlrlition in Watsr, Weltht'llo

VlscoaitJType 1 2 5 11

H 1,500-3,000 M 4,00CMl,500 G 150-400 J 150--400 L 75-150 E 150-700(b) El 150-300

Concentration in 283 Ethanol, Weight 'II,

http://www.herc.com/aqualon/personal_care/pc_uslit/pc_4175.html 7/08/2002

r·.

I Technical Data

VERSENE NA Disodium EDTA Chelating Agent

Product Name Typical Propertiea• VERSENE" NA Disodium EDTA chelating agen1 Product Availability North America, Latin America. Pacific, Europe, India. Middle E..t and Africa Applications food and beverage, phannaceuricals Active Ingredient Name Diaodium ethylenediaminetetrucetate dihydnte CAS Number 6381-92-6 '!fi Auay 99.0~•Ny\BDTA"2tf,O For TSCA purpose•, reference CAS No. 139-33--3 £or 89,4 ~ aa ~I\ECn'A anhydrous N~EDTA 77.7wt11taaH EOTA WI,ia, ID off-white powder Chemical Formula 980 "8fm1 er 61 lblcu ft C 11H,.N,O.Na,•2H,O or pH 4.3--4.7 (1 ~ oalulion) (NaOOCCH,)(HOOCCH,)NCH,Cff,N(CH,COOH) 4.0-6.0 (5 ~ aolulion) (CH2CCX>Na)•2H,O 6-7 ~ at 25oen7"F Chemical Structure HOOCCH2 \ 1cH,COONal [ NCH2CH2N 2H20

NaOOCCH2I ' CH2COOH EDTA allowed to be used in food products is specifically regulated by the US FDA. A.II such uses must conform to Molecular Weight the regulations. Disodium EDTA is considered a food 372.24 preservative in d.e US FDA n,gulationa. VERSENE NA Other Names disodium EDTA i,, Kosher and Pareve certified for Na,ff,EDTA•2H,0, Disodiwn EDTA PCC. Paaeover. Edetate Disodium USP Description For more information, complata literature, VERSENE NA Disodium EDTA chelating agent is a food and product samples. you can reach a Dow and pharmaceutical grade product which meets d.e require representative at the foNawing numbers: menh of the Food Cbemicale Codex and U.S. Pharma From the United States and Canada copeia XX.11. VERSENE NA chelating agent ia a partially call l-800.4"7-4369 • fax 1-989-832-1465 neutralized salt of EDT.A. in city form, and is suitable for direct food applications. It ia well suited for applications From Mexico calling for neutral pH or madly acidic conditioaa common a.II %-800-4.of7--4369 • f..,. 95-989-832-1465 to moat food and pharmaceutical produch. The principal function ofVERSENE NA chelating a,ent is to chemically In Europe toll-free +800.3694.6367 bind and render inactive those trace metals having .u, advene impact on the color, Ba.vor, clarity, shelf life, and call +32 3 450 2240 • fax +32 3 450 28l5 other important characteristics ol foods and pharmaceuti Or you can contact - on the Internet at cals. Literature references indicate synergy in antimicro www.versene.com bia.l activity. The applications and amount of diaodium Na41oe:Ho"-llam-,.,.--ti,-ar-...1111011e __ ..,._,__,. ____....,..._ __i-lilin10ano"* _ ....,change-time. CWlomerlll-lllble lOrdalamllnlng...,_praducsand Iha lnfannallanin lllladocumanl .,.,_...,.... 1arc.._,.1 ,_ and lar.-lringlhalC-s~andchpolalpradiclll.,.111~-appllcaDle------~-no abllpllan ar llallillly far Ille lnlarmalon in lllls clacunllm. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARMNTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCUJOEO. --June200i2 Pmled in U.S.A. 'Trademark al The Dow C-Campany Farm No. 113-0t340-602AMS ROQ.0ETTE a:.•c:rnCATJ:OJIS ..f, •n-OHG50

PJIGB 1/1 DISORBENE• LC

Di&f'D1fiOlr a

Dibensyliclene eomit:ol. · CAS a• 3264'1-'7-9 BD1BCS: 251-136-4

White pollder MCL OOU. 1.0 - 2.0 t NCL 1606A 96.S t min. NCL 095A (G/L) 150 - 350 g/1 MCL lJlC 224 - 228 degree•

Leatrem, January a. 2002 (j ROQUE'I-J•E IAPBTY DA'l'A SBBIIT llBF : I99-046G septt!lllber '9 - P 1/4, PRODUCf DISORBIDIB LC According to BBC/tl/155

1. CBDl[CIJ, •IIODUC'l' AIID oo•HIIT :n>Drn:1':ICA'l'IOll1 1.1 a.-ical product name...... DisoaBBIIB LC

1. 2 Supplier .•....••....•.•...... ROQUBiiB PRBUS Addre••· ...... ,211, ursnaa P1W1CB Telepbmle/Telefax •••....•.•..•.•.. 03.21.,3.]6.00 / 03.21.&3.ll.SO Blllergeac:y telephone •...... •.....• PUIICB 03.21.63.J,.oo / oJ.21.,J.JI.SO

2. ~J:TJ:OW/DIIOamanOII OIi J:NllDlmrS: 2 .1. Sub9tance ...••..•...... •...... •. • ye• 2.2 c:caaan cheaiaal aaae ...... 4ibensylidene aorbitol 2.3 OS DUllber ...... 32H7-67-9 2.4 Ingredient• contribu.tiag to tbe basard ...... •...... not applicable _I 3. RIZUDII 'tDDTJ:PJ:CATJ:0111 3.1 Most illportant basarda ..•••.....•. potentia1 for formation of explosive air / dust cloud 3.2 Specific hazard.a •••..••••.•.....•• exploaion bazarda. aee I 3.1 3.3 Other infOD1&tioo ..•••.•.•.....••• not claaaifiecl under Ol:IP J:eg\l].ation

1 , • n:an-am auuu9, ~ I . 4 .1 :Inhalation ..••...... remcn,e to fresh air; if symptcms develop. l aeeJt medical advice 4. 2 Bye contact .....•...•..•...... rinse with plenty of -ter ( 15 md 1 if irritation oecura. aeek medical attention 4 • 3 Skin CODtact •••••••••••••••••••••• wash with water and eoap. do aot uae organic aoheata 4 • 4 Ingeatian ..•...•...... ••..•....•• rinae mouth witb water, if irritation occurs, aeeJt medical attention 'I ,1 s. nu-naan:m auaus, 5.1 Bztingu.iahing -Ilia ...... water spray 5.2 lion-suitable eztinguiabing media •• C:02 : iaactiTe Pollder : basarda of duet cloud fozmatiaa

I. ACCD>DTAL RSLSU• ..UUU:81 6.1 Pereoaal precautioas ••••.•.•••.•.• follow rec Ddatiama for protectioo I I 6.2 1111Tiramaenta1 prec-tions .•...•... do noe rwa to clrai.D 6.3 Methods for cleaning up .....•..... collect aecbanical.ly aDl5 TllClllla the aoilecl if nec:esaary to eliainate residue•. aee I 13

7. DMDL%a AD IJTO&la 1 7.1 Halldling Teebnical measures ...... •...•.•• follow ttC"annendat-i0118 for personal protectian I 8 BOQUETTE IAl'Sff DATA IIID'.r • RBP : I'9-046G September 99 - P 2/4. PRODUCT DISORBBIIB LC Accordi119 to BBC/91/155

I Precautions .•••...••..•..•••.....• avoid du•t formation or disperaioa in the airl and keep away frca beat, flaae and spark 80lllCCe8 Safe handling advice ••••.••••.•..• follow general re~Ddatioae for banclling of duety product• "1.2 Storage Tecbnical measures ...... none Storage conditions •..•••...... • store in a cool, dry and well ventilated area, in -11 cloaed ccatainera Inc:c11p&tible producta •••...... •... •trong mcidiziag ag,uata Packaging -teriala .•••.•...... •.• fibEe dEWI with iuicle polytlHm bag

8. IIDOIIJltS 0011'l'aOLS/HUO•u. •JtCn'ICTJ:OJI: 8.1 Ccotrol par-tera ...... : follow the national regulation applicable to non specific total duata ABL <• 10 rag/ml (Prance) I 8.2 Personal protective equipnent I Reapiratory protection ••...•.•••.. dust -Bk in case of insufficient ventilation! Bye protection •..•...... ••. ·. appropriate goggles I Rand protection ••.•..•.••••..••... laperviows gloves Skin and body protection ...... •.. appropriate cloth recaaellded, a90id ccratact with tbe product l 8.3 &ygi- -aaures •••...... •..... general hygiene practices for cbellie&l products hand.ling

9. nT•:tCAL .aaD Cllaa:CAL IPROPDTID: 9. 1 Physical state ..••..••..•.•.•.•••• pollder COiour .....•...••..•••. ·•...... wbite Odour •••••••••••••••••••••••.••••• neutral 9.2 pH (concentratioa) •.•••.....•••..• not availabl.e, inaol.uble product 9.3 Boiling temperature ....••.....•..• not applicable Melting point ••••..••••..•••••.••• 22• - 22a •c Plasbpoint ..••...•..••..••.•..• , .. not applicable AutoignitiOD temperature •.....•..• 380 ·•C (00 - cloud) 9.4 Bxploai.on prapertiea •••...•...•... ain ignition energy approx 6.5 IIIJ ~ exploeiall pressure approx 8. 4 bara I UT approx 211 bar a/a I Cl-• (VDI 3673 ST) 2 I ain ezpl.oaible ooncentratioa: 30 - 60 g/ra3 (ref, nnatIS, si.ailar to Diaorbene) 9. s Denaity .•••.••.•.....•...•....•..• approx 0.25 kg/1 9.5 Solubility....•..•...... •...... inaoluble

I 10. ftU:tL:tff .um JIBACnffff: 110.1 Stability•••.•....••.•.... , •..•..• stable with respect to stOJ:11ge coaditiOllS 17 110.2 Hazardous reactiona .....•..•...... air/ dust miltture (ezploaion basarda) 110.3 Nateriala to avoid •.••..•..••.•... strong mtidiaing agents and •trcmg acids !10.4 Raaardoua decaapositlon products .. carbon -ide aad dioxide, benzaldebyde ROQU.ETTE BAl'ffl' DATA IIID'r • UP : 1'9-o,m September H - P 3/4, Acc:Ordlng DIS0118811B LC to BBC/91/155

I 111. 'IOUcm.oHCAL nm,aanoll: !11.1 Acute toxicity ..••••••••..•....••. oral LDSO in rat.a:> 2000 flll/SIJ 111. 2 t.oeal effect• •.••••.••.•••••..•••. EUIJbing -.y cau11e mecbaDic:al akin irritation I for byperN-itive individual• _111.3 Otber iafm:aatioa •...... •..•..•. DO lmollll todc:ity ·! 112. Z00L00%e&L J:IIIOmTIOII• 112.1 tersi•tance/Degradability•••••.••. aaa biodegradable product 1112.2 llc:otOlticity••••••••.•....•••...•.• a.so: not available . I I U • DXl'f08&L CIOll8J:DDA'l'J:Oll81 IU.1 ...te frca re•idue•-·············· caa be eliaiaated •• a 110lid waate ( ... ~ iadllatrial llellte) or incinerated in app.cowed treat:lmlt plant c:oofozaing with applicable I regulation• and legislation . I 113 • 2 Coa.taiDated packaging •••....•..•• llingle uae packaging I el:lai.-te or rec:ycl.e ac:cordiag to local. regulatiCIGII I IH. DWl'OD' D»om1'J:Olh 11,.1 International. regulatioaa ..••••..• not applicable 11,. 2 Ull DUllber ••••••••••••••••••••••••• D0Ge l RID/ADR R'l'MDR INDG U.TA/OM!I I CJ.a••· ...... •.....•...... D& na n a II a Gzou.p, number or page •.•..•...... Labelling ••••••.•••.••.•••...•••... Danger code ••••••••••.•••••••.•••. Product code •.••..•.••••••••••• ·••• I 115. DflOLA'IOD" J:lll'Om'n0Jr1 115.1 Labelling ac:ecmliag to BIIC 1 I •talldarda ...... not: ..... requincl I l 1laJlard ayabol •..••••.••.•.••....•. not applicable 115.2 LGc:a1 regu.laticaa .••...... •.•.• product c:oa.forming with following regulatioaa: • na - CPR 21: 11 176.170(c) • 177.1520(c) ROQUETTE llBF SAl'Bfl' DATA SDBT • ~ X99-0UG Septelllber tt - P 4/4 According DISOltBBMB LC to DC/91/155

l I 1'. oraa Illl'OIIAflOlh

BDIBCS: 251-13~-4

11ote: Thi• aulletin ca111Plete• the Technical Directiona for uM but ia not a 8111,atitute for 1:Jlea. Attention ia drawn to tile rlaks eacowitered when tbe in applicati0119 product ia Wied otber tluln tboae for which intended. It ia the reapoaaibility of t:be u-r to be aware of all4 to follow tbe regulati011.a applyuag to our product for its posae-iOD, baadling and u-. Ail infonation all4 i1U1t.ructioas prov-ided in tbi• safety Data Sheet (SDS) la made with no warranty I ; they axe baaed on tlle curxent state of our knoW1edge at the latest nviaion date indicated 011 the pre-at .. SDS.

! 1 1

! . !

Leat:r:at. 8 January 20G2 APPENDIX 11

Statistical Analysis for:

• Bar Mush

• Penetration

• Foam

• Syneresis

• Transparency Response: Bar Mush Transform: Natural log Constant: 0 *** WARNING: The Special Cubic Model is Aliased! ***

*** WARNING: The Cubic Model is Aliased! ***

Sequential Model Sum of Squares Sum of Mean F Source Squares DF Square Value Prob> F Mean 140.39 1 140.39 Linear 18.46 3 6.15 14.15 0.0002 Quadratic 4.81 .§_ 0.80 5.01 0.0203 Suggested Special Cubic0.96 3 0.32 5.01 0.0576 Aliased Cubic 0.000 0 Aliased Residual 0.32 5 0.064 Total 164.94 18 9.16

''Sequential Model Sum ofSquares": Select the highest order polynomial where the additional terms are significant and the model is not aliased.

Lack of Fit Tests Sum of Mean F Source Squares DF Square Value Prob > F Linear 5.77 9 0.64 10.03 0.0103 Quadratic 0. 96 J. 0.32 5.01 0.0576 Suggested Special Cubic0.000 0 Aliased Cubic 0.000 0 Aliased Pure Error 0.32 5 0.064

''Lack of Fit Tests": Want the selected model to have insignificant lack-of-fit.

Model Summary Statistics Std. Adjusted Predicted Source Dev. R-Squared R-Squared R-Squared PRESS Linear 0.66 0.7520 0.6988 0.6594 8.36 Quadratic 0.40 0.9479 0.8892 0.6062 9.67 Suggested Special Cubic0.25 0.9870 0.9557 + Aliased Cubic + Aliased + Case(s) with leverage of 1.0000: PRESS statistic not defined

"Model Summary Statistics": Focus on the model maximizing the "Adjusted R-Squared" and the "Predicted R-Squared". Response: Bar Mush Transform: Natural log Constant: 0 ANOVA for Mixture Reduced Quadratic Model Analysis of variance table [Partial sum of squares) Sum of Mean F Source Squares D F Square Value Prob > F Model 22.98 6 3.83 26.86 < 0.0001 significant Linear Mixture 12.53 3 4.18 29.30 <0.0001 AB 1.91 1 1.91 13.40 0.0038 AC 4.24 1 4.24 29. 72 0.0002 AD 4.30 1 4.30 30.18 0.0002 Residual 1.57 11 0.14 Lacko/Fit 1.25 6 0.21 3.26 0.1081 not significant Pure Error 0.32 5 0.064 Cor Total 24.55 17

The Model F-value of 26.86 implies the model is significant. There is only a 0.0 l % chance that a "Model F -Value" this large could occur due to noise.

Values of "Prob > F" less than 0.0500 indicate model terms are significant In this case Linear Mixture Components, AB, AC, AD are significant model terms. Values greater than 0.1000 indicate the model terms are not significant. If there are many insignificant model terms (not counting those required to support hierarchy), model reduction may improve your model.

The "Lack of Fit F-value" of 3 .26 implies the Lack of Fit is not significant relative to the pure error. There is a 10.81% chance that a "Lack of Fit F-value" this large could occur due to noise. Non-significant lack of fit is good -- we want the model to fit.

Std. Dev. OJ8 R-Squared 0.9361 Mean 2.79 Adj R-Squared 0.9013 CV. 13.52 Pred R-Squared 0.7925 PRESS 5.09 Adeq Precision 11.463

The "Pred R-Squared" of 0.7925 is in reasonable agreement with the "Adj R-Squared" of 0.9013.

"Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of 11.463 indicates an adequate signal. This model can be used to navigate the design space.

Coefficient Standard 95% Cl 95%CI Component Estimate DF Error Low High A-DBS 808.96 l 151.65 475.18 1142.75 B-HPC -1.73 19.52 -44.68 41.23 C-PG 3.91 0.25 3.35 4.47 D-GLY 3.94 0.25 3.38 4.49 AB -1420.52 388.08 -2274.68 -566.37 AC -900.40 165.16 -1263.92 -536.88 AD -896.30 163.14 -1255.37 -537.23

Final Equation in Terms of Pseudo Components:

Ln(Bar Mush) +808.96 *A -1.73 * B +3.91 *C +3.94 *D -1420.52 *A*B -900.40 *A*C -896.30 *A*D Final Equation in Terms of Real Components:

Ln(Bar Mush) +1484.37437 * DBS +3.56726 * HPC +4.84305 *PG +4.83014 *GLY -2574.06952 * DBS * HPC -1631.57805 *DBS* PG -1624.14408 *DBS* GLY

Final Equation in Terms of Actual Components:

Ln(Bar Mush) +19.86848 * DBS +0.047748 * HPC +0.064825 * PG +0.064652 * GLY -0.46117 *DBS*HPC -0.29231 *DBS*PG -0.29098 * DBS * GL Y

Diagnostics Case Statistics Standard Actual Predicted Student Cook's Outlier Run Order Value Value Residual Leverage Residual Distance t Order 1 3.91 3.86 0.053 0.1780. 153 0.001 0.147 6 2 1.76 1.83 -0.073 0.441-0.260 0.008 -0.248 9 3 3.91 381 0.10 0.4390.366 0.015 0.35 I 13 4 0.92 1.24 -0.32 0.456-1145 0.157 -1.163 11 5 3.91 3.91 l.532E-003 0.3500.005 0.000 0.005 10 6 2.34 2.10 0.24 0.4560.861 0.089 0.850 8 7 3.91 3.93 -0.022 0.432-0.078 0.001 -0.074 17 8 IJ2 1.29 0.031 0.4810.112 0.002 0.107 15 9 175 2.27 -0.52 0.435-1.831 0.369 -2.093 18 10 2.18 I.SO 0.69 0.4992.567 0.939 3.867 * 11 1.03 1.70 -0.67 0.361-2.209 0.394 -2.824 7 12 3.91 3.92 -6.620E-003 0. 175-0.019 0000 -0.018 5 13 3.91 3.92 -0.01 I 0.163-0.03 I 0.000 -0.030 14 14 1.67 1.24 044 0.4561.573 0.296 1.704 12 15 3.91 381 0.10 0.4390.366 0.015 0.35 I 2 16 3.91 3.93 -0.022 0.432-0.078 0.001 -0.074 4 17 2.09 2.10 -0.017 0.456-0.062 0.000 -0.059 16 18 3.91 3.91 l.532E-003 0.3500.005 0.000 0.005 3 * Case(s) with !Outlier TI > 3.50

Proceed to Diagnostic Plots (the next icon in progression). Be sure to look at the: I) Normal probability plot of the studentized residuals to check for normality of residuals. 2) Studentized residuals versus predicted values to check for constant error. 3) Outlier t versus run order to look for outliers, i.e, influential values. 4) Box-Cox plot for power transformations.

If all the model statistics and diagnostic plots are OK, finish up with the Model Graphs icon. Response: Penetration

Transform: Power Lambda: 2.63 Constant: 0 *** WARNING: The Special Cubic Model is Aliased! ***

*** WARNING: The Cubic Model is Aliased! ***

Sequential Model Sum of Squares Sum of Mean F Source Squares DF Square Value Prob > F Mean 3.708E+013 1 3.708E+013 Linear 1.741E+013 3 5.804E+0l2 23.94 < 0.0001 Quadratic 2.955E+012 §. 4.925E+0l 1 8.96 0.0034 Suggested Special Cubic 3.381E+0l 1 3 1.127E+0ll 5.55 0.0477 Aliased Cubic 0.000 0 Aliased Residual 1.016E+0l 1 5 2.031E+010 Total 5.789E+013 18 3.216E+0l2

''Sequential Model Sum ofSquares": Select the highest order polynomial where the additional terms are significant and the model is not aliased.

Lack of Fit Tests Sum of MeanF Source Squares DF Square Value Prob > F Linear 3.293E+012 9 3.659E+0l 1 18.02 0.0027 Quadratic 3.381E+0l 1 J. 1.127E+0ll 5.55 0.0477 Suggested Special Cubic 0.000 0 Aliased Cubic 0.000 0 Aliased Pure Error 1.016E+0l 1 5 2.031E+0l0

"Lack of Fit Tests": Want the selected model to have insignificant lack-of-fit.

Model Summary Statistics Std. Adjusted Predicted Source Dev. R-Squared R-Sq ua redR-Sq uared PRESS Linear 4.924E+005 0.8369 0.80190. 78364.502E+012 Quadratic 2.344E+005 0.9789 0.95510.84073.315E+Ol2Suggested Special Cubic 1.425E+005 0.9951 0. 9834 + Aliased Cubic + Aliased + Case(s) with leverage of 1.0000: PRESS statistic not defined

''Model Summary Statistics": Focus on the model maximizing the "Adjusted R-Squared" and the "Predicted R-Squared". Response: Penetration Transform: Power Lambda: 2.63 Constant: 0 ANOVA for Mixture Reduced Quadratic Model Analysis of variance table [Partial sum of squares] Sum of Mean F Source Squares DF Square Value Prob > F Model 2 016E+0l3 6 3.360E+Ol2 56.88 < 0.0001 significant Linear Mixture 1.405£+013 3 4.682£+012 79.27 < 0.0001 AB 6.905£+011 1 6.905£+011 11.69 0.0057 AC 2.694£+012 1 2.694£+012 45.60 < 0.0001 AD 2.727£+012 1 2.727£+012 46.17 <0.0001 Residual 6.497E+0l l 11 5.907E+0I0 Lacko/Fit 5.482£+011 6 9.136£+010 4.50 0.0601 not significant Pure Error 1.016£+011 5 2.031£+010 Cor Total 2.081E+0l3 17

The Model F-value of 56.88 implies the model is significant. There is only a 0.01% chance that a "Model F-Value" this large could occur due to noise.

Values of "Prob > F" less than 0.0500 indicate model terms are significant. In this case Linear Mixture Components, AB, AC, AD are significant model terms. Values greater than 0.1000 indicate the model terms are not significant. If there are many insignificant model terms (not counting those required to support hierarchy}, model reduction may improve your model.

The "Lack of Fit F-value" of 4.50 implies there is a 6.01 % chance that a "Lack of Fit F value" this large could occur due to noise. Lack of fit is bad-- we want the model to fit.

Std. Dev. 2.430E+005 R-Squared 0.9688 Mean l.435E+006 Adj R-Squared 0.9517 CV 16.93 Pred R-Squared 0.9114 PRESS l.844E+0l2 Adeq Precision 16 061

The "Pred R-Squared" of 0.9114 is in reasonable agreement with the" Adj R-Squared" of 0.9517.

"Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of 16.061 indicates an adequate signal. This model can be used to navigate the design space.

Coefficient Standard 95% Cl 95%CI Component Estimate DF Error Low High A-DBS 6.369E+008 9.762E+007 4.221E+008 8.518E+008 8-HPC -8. l 99E+006 l.256E+007 -3 .585E+007 l.945E+007 C-PG 2.601E+006 l.636E+005 2.241E+006 2.961E+006 D-GLY 2.433E+006 l.609E+005 2.078E+006 2.787E+006 AB -8.541E+008 2.498E+008 -l.404E+009 -3 .043E+008 AC -7. l 79E+008 l.063E+008 -9.5 l 9E+008 -4.839E+008 AD -7. l36E+008 l.050E+008 -9. 44 7E +008 -4.824E+008

Final Equation in Terms of Pseudo Components:

(Penetration)2-63 +6.369E+008 *A -8. l 99E+006 *B +2.601E+006 *C +2.433E+006 *D -8.541E+008 *A*B -7. l 79E+008 *A*C -7.136E+008 *A*D Final Equation in Terms of Real Components:

(Penetration)2- 63 + 1. 17248E +009 * DBS -9.40524E+006 * HPC +3.48277E+006 * PG +3.20288E+006 * GLY -1.54763E+009 *DBS* HPC -1.30089E+009 *DBS* PG -1.29303E+009 *DBS* GLY

Final Equation in Terms of Actual Components:

(Penetration)2-63 + l .56937E+007 * DBS -1.25890E+005 * HPC +46617.14383 *PG +42870.86386 *GLY -2. 77274E+005 *DBS* HPC -2.33068E+005 *DBS* PG -2.31660E+005 * DBS * GLY

Diagnostics Case Statistics Standard Actual Predicted Student Cook's Outlier Run Order Value Value Residual Leverage Residual Distance t Order 1 2.729E+006 2.489E+006 2.403E+005 0.1781.091 0.037 1.101 6 2 3.628E+005 4.312E+005 -68431.17 0.441-0.377 0.016 -0.361 9 3 2.408E+006 2.393E+006 15273.30 0.4390 084 0.001 0.080 13 4 l.726E+005 l.505E+005 22086.05 0.4560.123 0.002 0.118 11 5 2.361E+006 2 585E+006 -2.235E+005 0.350-1.141 0.100 -1.158 10 6 4.835E+005 5.473E+005 -63799.11 0.456-0.356 0.015 -0.341 8 7 2.553E+006 2.432E+006 1.211E+005 0.4320.661 0.047 0.643 17 8 3.929E+005 2.461E+005 1.468E+005 0.4810.838 0.093 0.826 15 9 4.007E+005 6.297E+005 -2.290E+005 0.435-1.254 0.173 -1.291 18 10 5.569E+005 l.834E+005 3.735E+005 0.4992.172 0.671 2.739 11 91510.43 5.958E+005 -5 043E+005 0361-2.596 0.543 -3.975 * 7 12 2.553E+006 2.534E+006 18960.75 0.1750.086 0.000 0.082 5 13 2.432E+006 2 509E+006 -77051.50 0.163-0.347 0.003 -0.332 14 14 2069E+005 l.505E+005 56416.69 0.4560.315 0.012 0.301 12 15 2.408E+006 2.393E+006 15273.30 0.4390.084 0.001 0.080 2 16 2.338E+006 2.432E+006 -94391.49 0.432-0.515 0.029 -0.497 4 17 6.792E+005 5.473E+005 l.319E+005 0.4560.736 0.065 0.720 16 18 2.704E+006 2.585E+006 1189E+005 0.3500.607 0.028 0.589 3 * Case(s) with !Outlier TI> 3.50

Proceed to Diagnostic Plots (the next icon in progression). Be sure to look at the 1) Normal probability plot of the studentized residuals to check for normality of residuals. 2) Studentized residuals versus predicted values to check for constant error. 3) Outlier t versus run order to look for outliers, i.e., influential values. 4) Box-Cox plot for power transformations.

If all the model statistics and diagnostic plots are OK, finish up with the Model Graphs icon. Response: Foam Volume *** WARNING: The Special Cubic Model is Aliased! ***

*** WARNING: The Cubic Model is Aliased! ***

Sequential Model Sum of Squares Sum of Mean F Source Squares DF Square Value Prob > F Mean 1.558E+006 1 1.558E+006 Linear 69207.55 3 23069.18 30.60 < 0.0001 Quadratic 8953. 75 6 1492.29 7.46 0.0061 Suggested Special Cubic 526.20 3 175.40 0.82 0.5379 Aliased Cubic 0.000 0 Aliased Residual 1075.00 5 215.00 Total 1.637E+006 18 90965.28

"Sequential Model Sum of Squares": Select the highest order polynomial where the additional terms are significant and the model is not aliased.

Lack of Fit Tests Sum of Mean F Source Squares DF Square Value Prob > F Linear 9479.95 9 1053.33 4.90 0.0474 Quadratic 526.20 l 175 40 0.82 0.5379 Sugg~st~g Special Cubic0.000 0 Aliased Cubic 0.000 0 Aliased Pure Error1075.00 5 215.00

''Lack ofFit Tests": Want the selected model to have insignificant lack-of-fit.

Model Summary Statistics Std. Adjusted Predicted Source Dev. R-Squared R-Squared R-Squared PRESS Linear 27.46 0.8677 0.8393 0.7818 17402.90 Quadratic 14.15 0.9799 0.9573 0.8795 9608.39 Suggested Special Cubic 14.66 0.9865 0.9542 + Aliased Cubic + Aliased + Case(s) with leverage of 1.0000: PRESS statistic not defined

"Model Summary Statistics": Focus on the model maximizing the "Adjusted R-Squared" and the "Predicted R-Squared". Response: Foam Volume ANOVA for Mixture Reduced Quadratic Model Analysis of variance table [Partial sum of squares] Sum of Mean F Source Squares DF Square Value Prob > F Model 78055 04 6 13009.17 83.81 < 0.0001 significant Linear Mixture 72229.26 3 24076.42 155.11 < 0.0001 AC 695.67 1 695.67 4.48 0.0579 AD 703.12 1 703.12 4.53 0.0567 CD 4426.98 1 4426.98 28.52 0.0002 Residual 1707.46 11 155.22 Lacko/Fit 632.46 6 105.41 0.49 0.7946 not significant Pure Error 1075.00 5 215.00 Cor Total 79762.50 17

The Model F-value of 83 .81 implies the model is significant. There is only a 0.01 % chance that a "Model F -Value" this large could occur due to noise.

Values of "Prob > F" less than 0.0500 indicate model terms are significant. In this case Linear Mixture Components, CD are significant model terms. Values greater than 0. 1000 indicate the model terms are not significant. If there are many insignificant model terms (not counting those required to support hierarchy), model reduction may improve your model.

The "Lack of Fit F-value" of 0.49 implies the Lack of Fit is not significant relative to the pure error. There is a 79.46% chance that a "Lack of Fit F-value" this large could occur due to noise. Non-significant lack of fit is good-- we want the model to fit.

Std. Dev. 12.46 R-Squared 0.9786 Mean 294.17 Adj R-Squared 0.9669 c.v. 4.24 Pred R-Squared 0.9407 PRESS 4728.00 Adeq Precision 28.300

The "Pred R -Squared" of 0. 9407 is in reasonable agreement with the "Adj R-Squared" of 0. 9669.

"Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of 28.300 indicates an adequate signal. This model can be used to navigate the design space.

Coefficient Standard 95% Cl 95%CI Component Estimate DF Error Low High A-DBS 852101 1 4437.63 -1246.13 18288.16 8-HPC -1048.02 487.33 -2120.61 24.58 C-PG 340.42 10.54 317.23 363.61 D-GLY 445.41 8.80 426.05 464.76 AC -10348.84 4888.42 -21108.19 410.51 AD -10126.50 4757.98 -20598.76 345.75 CD -259.51 48.59 -366.46 -152.56

Final Equation in Terms of Pseudo Components:

Foam Volume +8521.01 *A -1048.02 *B +340.42 *C +445.41 *D -10348.84 *A*C -10126.50 *A*D -259.51 *C*D Final Equation in Terms of Real Components:

Foam Volume +15808.11384 * DBS -1668.43728 * HPC +443.84370 *PG +464.70502 *GLY -18752.67843 *DBS* PG -18349. 78759 * DBS * GLY -470.24664 * PG * GL Y

Final Equation in Terms of Actual Components:

Foam Volume +211.59301 * DBS -22.33218 * HPC +5.94089 *PG +6.22012 *GLY -3.35974 *DBS*PG -3.28756 *DBS* GLY -0.084250 * PG* GLY

Diagnostics Case Statistics Standard Actual Predicted Student Cook's Outlier Run Order Value Value Residual Leverage Residual Distance t Order I 310.00 316.31 -6.31 0.195-0.564 0.011 -0.546 6 2 230.00 230.51 -0.51 0.449-0.055 0.000 -0.053 9 3 310.00 304.96 5.04 0.2970.482 0.014 0.465 13 4 235.00 222.75 12.25 0.3891.257 0.144 1.296 11 5 340.00 327.66 12.34 0.3331.213 0.105 1.243 10 6 245.00 230.66 14.34 0.3601.439 0.167 1.523 8 7 440.00 442.63 -2.63 0.478-0.293 0.011 -0.280 17 8 260.00 254.86 5.14 0.4070.535 0.028 0.517 15 9 230.00 235.52 -5.52 0.376-0.561 0.027 -0.542 18 10 300.00 291.50 8.50 0.5130.978 0.144 0.975 1 11 240.00 255.60 -15.60 0.482-1.740 0.403 -1.949 7 12 320.00 319.98 0.024 0.3890.002 0.000 0.002 5 13 345.00 333.41 11.59 0.4741.283 0.212 1.326 14 14 210.00 222.75 -12.75 0.389-1.310 0.156 -1.359 12 15 310.00 304.96 5.04 0.2970.482 0.014 0.465 2 16 440.00 442.63 -2.63 0.478-0.293 O.Oll -0.280 4 17 220.00 230.66 -10.66 0.360-1.069 0.092 -1.077 16 18 310.00 327.66 -17.66 0.333-1.735 0.215 -1.941 3

Proceed to Diagnostic Plots (the next icon in progression). Be sure to look at the: 1) Normal probability plot of the studentized residuals to check for normality of residuals. 2) Studentized residuals versus predicted values to check for constant error. 3) Outlier t versus run order to look for outliers, i.e., influential values. 4) Box-Cox plot for power transformations.

If all the model statistics and diagnostic plots are OK, finish up with the Model Graphs icon. Response: Syneresis

*** WARNING: The Special Cubic Model is Aliased! ***

*** WARNING: The Cubic Model is Aliased! ***

Sequential Model Sum of Squares Sum of Mean F Source Squares DF Square Value Prob > F Mean 568.97 l 568.97 Suggested Linear 2.88 3 0.96 1.80 0.1934 Quadratic 5.20 6 0.87 3.06 0.0734 Suggested Special Cubic 2.16 3 0.72 32.11 0.0011 Aliased Cubic 0.000 0 Aliased Residual 0.11 5 0.022 Total 579.32 18 32.18

"Sequential Model Sum of Squares": Select the highest order polynomial where the additional terms are significant and the model is not aliased.

Lack of Fit Tests Sum of Mean F Source Squares DF Square Value Prob > F Linear 7.36 9 0.82 36.53 0.0005 Quadratic 2.16 .l 0.72 32 11 0 0011 Suggest~g Specnl Cubic0.000 0 Aliased Cubic 0.000 0 Aliased Pure Error O. 11 5 0.022

"lack ofFit Tests": Want the selected model to have insignificant lack-of-fit.

Model Summary Statistics Std. Adjusted Predicted Source Dev. R-Squared R-Squared R-Squared PRESS Linear 0.73 0.2783 0.1237 -0.1230 11.62 Quadratic 0.53 0.7809 0.5344 -2.3235 34.40 Suggested Special Cubic0.15 0.9892 0.9632 + Aliased Cubic + Aliased + Case(s) with leverage of 1.0000: PRESS statistic not defined

''Model Summary Statistics": Focus on the model maximizing the "Adjusted R-Squared" and the "Predicted R-Squared". Response: Moisture Absorption ANOVA for Mixture Reduced Quadratic Model Analysis of variance table [Partial sum of squares] Sum of Mean F Source Squares DF Square Value Prob > F Model 8.08 7 1.15 5.09 0.0108 significant Linear Mixture 2.61 3 0.87 3.83 0.0462 AB 1.05 1 1.05 4.65 0.0565 AD 2.31 1 2.31 10.18 0.0096 BC 1.06 1 1.06 4.67 0.0560 BD 1.05 1 1.05 4.64 0.0567 Residual 2.27 10 0.23 Lacko/Fit 2.16 5 0.43 19.27 0.0028 significant Pure Error 0.11 5 0.022 Cor Total 10.35 17

The Model F-value of 5.09 implies the model is significant. There is only a I .08% chance that a "Model F-Value" this large could occur due to noise.

Values of "Prob > F" less than 0.0500 indicate model terms are significant. In this case Linear Mixture Components, AD are significant model terms. Values greater than 0. 1000 indicate the model terms are not significant. If there are many insignificant model terms (not counting those required to support hierarchy), model reduction may improve your model.

The "Lack of Fit F-value" of 19.27 implies the Lack of Fit is significant. There is only a 0.28% chance that a "Lack of Fit F-value" this large could occur due to noise. Significant lack of fit is bad-- we want the model to fit.

Std. Dev. 0.48 R-Squared 0.7808 Mean 5.62 Adj R-Squared 0.6274 CV 8.47 Pred R-Squared 0.0303 PRESS 10.04 Adeq Precision 7.714

The "Pred R-Squared" ofO 0303 is not as close to the "Adj R-Squared" of 0.6274 as one might normally expect. "Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of 7. 714 indicates an adequate signal. This model can be used to navigate the design space.

Coefficient Standard 95% Cl 95%CI Component Estimate DF Error Low High A-DBS -5.356E-003 5.62 -12.52 12.51 B-HPC 10101.41 4671.62 -307.61 20510.43 C-PG 5.56 0.33 4.82 6.31 D-GLY 5.54 0.32 4.84 6.25 AB -10135.52 470207 -20612.38 341.34 AD 45.17 14.15 13.63 76.70 BC -10295.90 4764.28 -20911.38 319.57 BD -10042.15 4662.37 -20430.55 346.25

Final Equation in Terms of Pseudo Components:

Moisture Absorption -5 .356E-003 *A +10101.41 *B +5.56 *C +5.54 *D -10135.52 *A*B +45.17 *A*D -10295.90 *B*C -10042.15 *B*D

Final Equation in Terms of Real Components:

Moisture Absorption -22.23503 * DBS + 18276.10591 * HPC +5.75867 * PG +5.18142 *GLY -18366.12647 * DBS * HPC +81.84454 *DBS* GLY -18656.74919 * HPC * PG -18196.92971 * HPC * GLY

Final Equation in Terms of Actual Components:

Moisture Absorption -0.29762 * DBS +244.62730 * HPC +o.077080 *PG +0.069354 *GLY -3.29049 *DBS* HPC +0.014663 *DBS* GLY -3.34255 * HPC * PG -3.26017 * HPC * GLY

Diagnostics Case Statistics Standard Actual Predicted Student Cook's Outlier Run Order Value Value Residual Leverage Residual Distance t Order I 5.50 4.80 0.70 0 5052 084 0.553 2.629 6 2 6.50 6.99 -0.49 0.681-1.806 0.872 -2.088 9 3 5.50 5.67 -0.17 0.481-0.498 0.029 -0.478 13 4 5.23 5.08 0.15 0.4890.427 0.022 0.409 11 5 5.50 5.56 -0062 0.380-0.165 0.002 -0.156 10 6 5.05 5.18 -0.13 0.477-0.372 0.016 -0.355 8 7 5.45 5.55 -0.100 0.431-0.278 0.007 -0.264 17 8 3.75 4.63 -0.88 0.514-2.658 0.932 -4.655 * 15 9 6.70 6.82 -0.12 0.619-0.401 0.033 -0.383 18 10 7.58 7.08 0.50 0.4121.363 0.163 1.433 I 11 6.17 5.68 0.49 0.4011.320 0.146 1.379 7 12 5.50 5.56 -0.055 0.184-0.128 0.000 -0.122 5 13 5.50 5.55 -0.052 0.166-0.120 0.000 -0.113 14 14 5.25 5.08 0.17 0.4890.486 0.028 0.466 12 15 5.50 5.67 -0.17 0.481-0.498 0.029 -0.478 2 16 5.50 5.55 -0.050 0.431-0.138 0.002 -0.131 4 17 5.52 5.18 034 0.4770.993 0.113 0.993 16 18 5.50 5.56 -0062 0.380-0.165 0.002 -0. 156 3 * Case(s) with !Outlier TI> 3.50

Proceed to Diagnostic Plots (the next icon in progression). Be sure to look at the: I) Normal probability plot of the studentized residuals to check for normality of residuals. 2) Studentized residuals versus predicted values to check for constant error. 3) Outlier t versus run order to look for outliers, i.e., influential values. 4) Box-Cox plot for power transformations.

If all the model statistics and diagnostic plots are OK, finish up with the Model Graphs icon. Response: Transparency *** WARNING: The Special Cubic Model is Aliased! ***

*** WARNING: The Cubic Model is Aliased! ***

Sequential Model Sum of Squares Sum of Mean F Source Squares DF Square Value Prob > F Mean 378.13 1 378.13 Linear 121.84 J 40.61 64.73 < 0.0001 Suggested Quadratic 6.09 6 1.02 3.02 0.0756 Special Cubic 1.57 3 0.52 2.32 0.1925 Aliased Cubic 0.000 0 Aliased Residual 1.12 5 0.22 Total 508.75 18 28.26

''Sequential Model Sum of Squares": Select the highest order polynomial where the additional terms are significant and the model is not aliased.

Lack of Fit Tests Sum of Mean F Source Squares DF Square Value Prob > F Linear 7.66 2. 0.85 3.78 0.0785 Suggested Quadratic I. 57 3 0.52 2.32 0.1925 Special Cubic0.000 0 Aliased Cubic 0.000 0 Aliased Pure Error 1. 13 5 0.23

''Lack of Fit Tests": Want the selected model to have insignificant lack-of-fit.

Model Summary Statistics Std. Adjusted Predicted Source Dev. R-Squared R-Squared R-Squared PRESS Linear 0.79 0.9328 0.9183 0.8901 14.36 Suggested Quadratic 0.58 0.9794 0.9562 0.9176 10.76 Special Cubic0.47 0.9914 0.9707 + Aliased Cubic + Aliased + Case(s) with leverage of 1.0000: PRESS statistic not defined

''Model Summary Statistics": Focus on the model maximizing the "Adjusted R-Squared" and the "Predicted R-Squared". Response: Transparency ANOV A for Mixture Linear Model Analysis of variance table [Partial sum of squares] Sum of Mean F Source Squares DF Square Value Prob > F Model 121.84 3 40.61 64. 73 < 0.0001 significant Linear Mixture 121.84 3 40.61 64.73 < 0.0001 Residual 8.78 14 0.63 Lacko/Fit 7.66 9 0.85 3.78 0.0785 not significant Pure Error 1.13 5 0.23 Cor Total 130.62 17

The Model F-value of 64. 73 implies the model is significant. There is only a 0.01 % chance that a "Model F-Value" this large could occur due to noise.

Values of"Prob > F" less than 0.0500 indicate model terms are significant. In this case Linear Mixture Components are significant model terms. Values greater than 0. 1000 indicate the model terms are not significant. If there are many insignificant model terms (not counting those required to support hierarchy), model reduction may improve your model.

The "Lack of Fit F-value" of 3. 78 implies there is a 7.85% chance that a "Lack of Fit F value" this large could occur due to noise. Lack of fit is bad-- we want the model to fit.

Std. Dev. 0.79 R-Squared 0.9328 Mean 4.58 Adj R-Squared 0.9183 CV 17.28 Pred R-Squared 08901 PRESS 14.36 Adeq Precision 18.961

The "Pred R-Squared" of 0.8901 is in reasonable agreement with the "Adj R-Squared" of 0.9 I 83

"Adeq Precision" measures the signal to noise ratio. A ratio greater than 4 is desirable. Your ratio of 18. 961 indicates an adequate signal. This model can be used to navigate the design space.

Coefficient Standard 95% Cl 95%CI Component Estimate DF Error Low High A-DBS 74.29 I 5.05 63.45 85.13 B-HPC -2.29 28.76 -63.98 59.40 C-PG 1.27 0.44 0.34 2.21 D-GLY 4.10 0.45 3.13 5.07

Adjusted Adjusted Approx t for II) Component Effect DF Std Error Effect=0 Prob > ltl A-DBS 5.94 0.90 6.58 < 0.0001 B-HPC -0.52 0.52 -0.99 0.3368 C-PG -21.70 8.95 -242 0.0294 D-GLY -20.17 9.43 -2 14 0.0506

Final Equation in Terms of Pseudo Components:

Transparency +74.29 *A -2.29 *B +1.27 *C +4.10 *D

Final Equation in Terms of Real Components: Transparency +97.94985 * DBS -5.13930 * HPC -0.33624 *PG +3.47014 *GLY

Final Equation in Terms of Actual Components:

Transparency +1.31107 * DBS -0.068790 * HPC -4.50055E-003 *PG +0.046448 *GLY

Diagnostics Case Statistics Standard Actual Predicted Student Cook's Outlier Run Order Value Value Residual Leverage Residual Distance t Order I 1.00 150 -0.50 0.150-0.681 0.021 -0.668 6 2 8.00 8.46 -0.46 0.213-0.657 0.029 -0.643 9 3 1.00 1.44 -0.44 0.273-0.651 0.040 -0.637 13 4 8.00 7.13 0.87 0.2641.279 0.146 1.312 11 5 1.00 156 -0.56 0.242-0.805 0.052 -0.794 10 6 8.00 7.25 0.75 0.2831.124 0125 1.136 8 7 5.00 4.08 0.92 0.3231.409 0.236 1.465 17 8 4.50 4.34 0.16 0.0890.208 0.001 0.201 15 9 8.00 8.52 -0.52 0.217-0.741 0.038 -0.729 18 10 6.00 7.39 -1.39 0.200-1.965 0.241 -2.226 I II 4.50 4.16 034 0.0880.444 0.005 0.431 7 12 4.00 2.40 1.60 0.1392.181 0.193 2.586 5 13 3.00 2.82 0.18 0. 1370.247 0.002 0.238 14 14 7.50 7.13 037 0.2640.544 0.026 0.529 12 15 1.00 1.44 -0.44 0.273-0.651 0.040 -0.637 2 16 4.00 4.08 -0.082 0.323-0.125 0.002 -0.121 4 17 7.00 7.25 -0.25 0.283-0.366 0013 -0.355 16 18 1.00 156 -0.56 0.242-0.805 0.052 -0.794 3

Proceed to Diagnostic Plots (the next icon in progression). Be sure to look at the I) Normal probability plot of the studentized residuals to check for normality of residuals. 2) Studentized residuals versus predicted values to check for constant error. 3) Outlier t versus run order to look for outliers, i.e., influential values. 4) Box-Cox plot for power transformations.

If all the model statistics and diagnostic plots are OK, finish up with the Model Graphs icon. APPENDIX12

Rheology Modifiers and their Solubility in Propylene Glycol

U,UNF U,UNF

Gum Gum

Gums Gums

NAME NAME

Polenc/Jaguar Polenc/Jaguar

Rhone Rhone

Gum Gum

rcol rcol

Aqualon/Supe Aqualon/Supe

Meer Meer

TIC TIC

Meer Meer

DE DE

TIC TIC

SUPPLIER/TRA SUPPLIER/TRA

or or

gels gels

and and

glycol glycol

gum gum

yields yields

ions ions

borate borate

metal metal

Form Form

crosslinked, crosslinked,

with with

viscoelastic viscoelastic

pseudoplastic pseudoplastic

emulsions emulsions propylene propylene

alginate alginate

Xanthan Xanthan

SYNERGISM SYNERGISM

NIA NIA

at at

most most

salt salt

and and

of of

affect affect

soln soln

ION ION

stability stability

may may

TOLERANCE TOLERANCE

viscosity viscosity

multivalent multivalent

hydration hydration

but but

pH=5. pH=5. Tolerant Tolerant

Max Max

viscosity viscosity

decrease decrease

Electrolytes Electrolytes

with with

10.5 10.5

PH PH

RANGE RANGE

STABLE STABLE

3.5 3.5

multivalent multivalent

Reacts Reacts salts salts

5-9 5-9

SOLUTION SOLUTION

CLARITY CLARITY

Translucent Translucent

OF OF

NIA NIA

and and

viscous viscous

on-newtonian, on-newtonian,

RHEOLOGY RHEOLOGY

Elastic Elastic VISCOUS VISCOUS

Pseudoplastic, Pseudoplastic,

mucilage. mucilage.

Forms Forms

Pseudoplastic. Pseudoplastic.

reversible reversible

thermally thermally N N

thixotropic thixotropic

of of

in in

ethanol ethanol

Soluble Soluble

GLYCOL GLYCOL

Solubility Solubility

miscible miscible

Tolerant Tolerant

70% 70%

Not Not

water-

Soluble Soluble

solvents solvents

PROPYLENE PROPYLENE

Tolerant Tolerant

Not Not

Tolerant Tolerant

water water

WATER WATER

Solubility Solubility

Soluble Soluble

but but

swellable swellable

Not Not

Poor Poor

solubility solubility

urens urens

from from

shrubs. shrubs.

of of

from from

acidic acidic

of of

partially partially

and and

of of

molecular molecular

complex complex

seed seed

MISTRY MISTRY

available available

SOURCE/CHE SOURCE/CHE

Cyamopis Cyamopis

legume legume

polysaccharide polysaccharide

tetragonolobus. tetragonolobus. Branched Branched

the the Slightly Slightly

acidic acidic

obtained obtained

polvsaccharide polvsaccharide

Astragalus Astragalus neutral neutral salt, salt,

Exudate Exudate

mixture mixture

Exudate Exudate

polysaccharide. polysaccharide.

genus genus

weight, weight,

tree. tree.

acetylated acetylated

Sterculia Sterculia

High High

Polymers Polymers

not not

data data

A A

NI NI

Natural Natural

Polymers Polymers

exudate) exudate)

Extract) Extract)

exudate) exudate)

KARAYAGUM KARAYAGUM

GUARGUM GUARGUM

TRAGACANTH TRAGACANTH

I. I.

3. 3.

(Seed (Seed

GUM GUM 2. 2.

(Shrub (Shrub

(Tree (Tree

THICKENER- Natural Natural

high high

488T) 488T)

and and

Gum Gum

NAME NAME

TH-11 TH-11

co co

Hercules/Genuvis Hercules/Genuvis

(Colloid (Colloid

viscosity) viscosity)

TIC TIC

Kelco/Kelcoloid Kelco/Kelcoloid

(low (low

LVFandHVF LVFandHVF

DE DE

SUPPLIER/TRA SUPPLIER/TRA

and and

gel gel

elastic elastic

and and

soft, soft,

bean bean

with with

imparts imparts

Xanthan Xanthan

value value

cohesive, cohesive,

gels gels

kappa-

maximum maximum

Xanthan Xanthan

Locust Locust strength strength

kappa-

Strong Strong

pseudoplasticity. pseudoplasticity.

increase increase

Gum Gum

With With

yield yield

SYNERGISM SYNERGISM

salts salts

Cation Cation

upon upon

in in

iota, iota,

may may

alent alent

ION ION

Ca, Ca,

sensitivity-

TOLERANCE TOLERANCE

lambda, lambda,

kappa kappa

Inc Inc precipitation precipitation

gelation, gelation,

resulting resulting

crosslink, crosslink,

Esp Esp

Polyvalent Polyvalent

viscosity viscosity storage. storage.

increases increases

Monov Monov

9 9

PH PH

RANGE RANGE

STABLE STABLE

3.5-

5-10 5-10

SOLUTION SOLUTION

CLARITY CLARITY

OF OF

at at

start start

0.5% 0.5%

starts starts

of of

at at

concn. concn.

cation, cation,

gels gels

guluronic guluronic

form form

brittle brittle

RHEOLOGY RHEOLOGY

Rigid Rigid

to to 0.04% 0.04%

Gelation Gelation

elastic elastic mannuronic mannuronic

High High ratio ratio

- MSandM:G MSandM:G

High High

gelling gelling

Function Function

to to

of of

up up

40% 40%

water-

Soluble Soluble

Solubility Solubility

NIA NIA

upto upto

solvent solvent

Compatibility Compatibility

organic organic

Not Not

70% 70%

miscible miscible solvents solvents

Not Not Tolerant Tolerant

GLYCOL GLYCOL

PROPYLENE PROPYLENE

in in

WATER WATER

Solubility Solubility

water water

boiling boiling Soluble Soluble

Soluble Soluble

acid acid

alpha alpha

algae algae

with with

of of

linked linked

available available

of of

from from

genera genera

from from

seaweed seaweed

class class

units. units.

beta beta

guluronic guluronic

not not

MISTRY MISTRY

marine marine

the the

Rhodophvcea Rhodophvcea

several several

of of Extrac Extrac SOURCE/CHE SOURCE/CHE

of of

arrangement. arrangement.

and and

alternating alternating

residues residues

acid acid

Galactan Galactan

and and

mannuronic mannuronic

seaweed. seaweed.

galactose galactose

mixture mixture derived derived

polysaccharide polysaccharide Straight-chain Straight-chain

Consists Consists brown brown

derived derived polysaccharide polysaccharide Straight-chain Straight-chain

Polymers Polymers

data data

A A -

NI NI

Natural Natural

Extract) Extract)

Polymers Polymers

AGAR AGAR

CARRAGEENAN CARRAGEENAN

ALGINATES ALGINATES

6. 6.

5. 5.

(Seaweed (Seaweed

4. 4.

Natural Natural THICKENER-

QP QP

330 330

Plus Plus

430. 430.

PCG-10 PCG-10

grade grade

and and

CS CS

Aqualon Aqualon

Aqualon-

and and

Natrosol Natrosol

Cellosize Cellosize

Aqualon Aqualon

RADE RADE

SUPPLIER/f SUPPLIER/f

NAME NAME

with with

a a

form form

groups groups

stability stability

polymer polymer

micelles) micelles)

mixed mixed

with with

surfactant-

surfactants surfactants

Association Association

boding boding

(associate (associate c c

of of

to to

hydrophobi hydrophobi

hydrogen hydrogen

be be

l. l.

2. 2.

mechanisms: mechanisms:

Thickening Thickening

problem problem

may may

amphoterics amphoterics

Heat Heat

SYNERGISM SYNERGISM

ions. ions.

-not -not

by by

ION ION

TOLERANCE TOLERANCE

multivalent multivalent

affected affected

Nonionic-not Nonionic-not

multivalent multivalent

Non-ionic Non-ionic

affected affected

cellulosic cellulosic

Non-ionic Non-ionic

PH PH

TY TY

STABILI STABILI

2-11 2-11

4-10 4-10

OF OF

CLARITY CLARITY

SOLUTION SOLUTION

Transparent Transparent

DS DS

for for

in in

with with

solution solution

efficient efficient

RHEOLOGY RHEOLOGY

Pseudoplastic. Pseudoplastic.

pseudoplastic pseudoplastic

decrease decrease

increase increase

thickener thickener

formulations formulations

aqueous aqueous

Highly Highly

viscous viscous

Highly Highly Pseudoplastic Pseudoplastic

Thixotrohpy Thixotrohpy

Soluble Soluble

Soluble Soluble Soluble Soluble

Tolerant Tolerant

Solubility Solubility

Not Not

PROPYLENE PROPYLENE

GLYCOL GLYCOL

But But

Not Not Not Not

Tolerant Tolerant

WATER WATER

Solubility Solubility

Soluble Soluble

Soluble Soluble Soluble Soluble

(three (three

with with

Polymers Polymers

polymer polymer

cellulose cellulose

hydroxyl hydroxyl

ionic ionic

reacting reacting

polymer polymer

nonionic nonionic

an an

available available

groups) groups)

by by

oxide. oxide.

terminal terminal ring ring

carboxymethyl carboxymethyl

SOURCE/ SOURCE/

cellulose cellulose

or or

CHEMISTRY CHEMISTRY

not not

Natural Natural

cellulose, cellulose,

Sodium Sodium

water-soluble water-soluble

reactive reactive

Non-ionic Non-ionic

prepared prepared

sites, sites, ethylene ethylene

alkali alkali

hydroxyethyl hydroxyethyl

modified. modified.

hvdroxvl hvdroxvl Hydrophobically Hydrophobically

data data

A - A

Modified Modified

NI NI

Natural Natural

ELLULOSE ELLULOSE

Polymers Polymers

Modified Modified

THICKENER-

8. 8.

LCELLULOSE LCELLULOSE

(HMHEC) (HMHEC)

GUM(CMC) GUM(CMC)

7. 7.

(HEC) (HEC)

CELLULOSE CELLULOSE

HYDROXYETHY HYDROXYETHY

9.CETYL 9.CETYL YDROXYETHYL YDROXYETHYL

MP MP

M M

Rhone Rhone

sol sol

Poulenc/Jaguar Poulenc/Jaguar

Aqualon/Galacta Aqualon/Galacta

Aqualon/Klucel Aqualon/Klucel

Benecel Benecel

Aqualon Aqualon

methylcellulose methylcellulose

Benecel Benecel

Aqualon Aqualon 1500 1500

Hydroxypropyl Hydroxypropyl

cellulose: cellulose:

Hydroxymethyl Hydroxymethyl

PolymerHM-

Amercell Amercell

Amercholl Amercholl

SUPPLIER/TRA SUPPLIER/TRA

DENAME DENAME

with with

other other

interact interact

HMHEC HMHEC

of of

as as

will will

nonoxynol nonoxynol

compatibility compatibility range range

amphoterics amphoterics

Nonionic-broad Nonionic-broad

compatibility compatibility

Excellent Excellent

ingredients ingredients

groups groups hydrophobic hydrophobic

differently differently

HEC HEC

Same Same but but

SYNERGISM SYNERGISM

not not

by by

CE CE

ION ION

improves improves

TOLERAN TOLERAN

tolerance. tolerance.

derivatizatio derivatizatio

n n

salt salt

HP HP

ions ions

multivalent multivalent

affected affected

Nonionic-

generally generally

NIA NIA

PH PH

!TY !TY

3.5-11 3.5-11

2-11 2-11

STABIL STABIL

NIA NIA

clear clear

SOLUTION SOLUTION

CLARITY CLARITY

OF OF

NIA NIA

Sparkingly Sparkingly

Transparent Transparent

lubricious. lubricious.

RHEOLOGY RHEOLOGY

Pseudoplastic, Pseudoplastic,

highly highly

Pseudoplastic, Pseudoplastic,

nonthixotropic nonthixotropic

Pseudoplastic Pseudoplastic

nonthixotropic nonthixotropic

Pseudoplastic Pseudoplastic

Soluble Soluble

Solubility Solubility

GLYCOL GLYCOL

Not Not

Soluble Soluble

Not Not

PROPYLENE PROPYLENE

NIA NIA

in in

water water

WATER WATER

Solubility Solubility

Soluble Soluble

Soluble-hot Soluble-hot

Soluble-

cold cold

Not Not Soluble Soluble

Soluble Soluble

hot hot

cold cold

Not Not

NIA NIA

in in

with with

but but

Polymers Polymers

1 1

more more

as as

pendant pendant

group group

reacting reacting

attach attach

oxide oxide

propylene propylene

polymer polymer

by by

much much

may may

a a

phenol phenol

manner manner synthesis synthesis

available available

SOURCE/ SOURCE/

substituted substituted

with with

1 1

CHEMISTRY CHEMISTRY

Natural Natural

droxypropy droxypropy

not not

oxide oxide

prepared prepared

guar guar character character

propylene propylene

hydrophobic hydrophobic

HEC HEC Nonionic Nonionic

yields yields

same same groups groups

Hy Hy

nony nony

HEC HEC

hydrophobic hydrophobic

data data

A A

NI NI

Modified Modified

Natural Natural

CELLULOSE CELLULOSE

METHYL METHYL

13. 13.

12. 12.

HYDROXYPROP HYDROXYPROP

YLGUAR YLGUAR

(HPC) (HPC)

11. 11.

HYDROXYPROP HYDROXYPROP

YL YL

10. 10.

CELLULOSE CELLULOSE Polymers Polymers

LCELLULOSE LCELLULOSE

Modified Modified

HYDROXYETHY HYDROXYETHY NONOXYNOL NONOXYNOL THICKENER-

Goodrich/ Goodrich/

Goodrich Goodrich

Chemicals/Hypa Chemicals/Hypa

n n Lipo Lipo

Pemulen Pemulen

BF BF

Rheox/Rheolate Rheox/Rheolate

BF BF

ADENAME ADENAME SUPPLIER/TR SUPPLIER/TR

NIA NIA

SYNERGISM SYNERGISM

to to

and and

better better

but but

ionic ionic

salts salts

NIA NIA

carbomers carbomers

ION ION

tolerance tolerance

Low Low

tolerance. tolerance.

Poor Poor

electrolyte electrolyte

surfactant surfactant

than than

generally generally

TOLERANCE TOLERANCE

Low Low

=>5 =>5

PH PH

TY TY

5-10 5-10

STABILI STABILI

clear clear

Clear Clear

SOLUTION SOLUTION

CLARITY CLARITY

Sparkling Sparkling

OF OF

pseudoplastic pseudoplastic

Thixotropic Thixotropic

RHEOLOGY RHEOLOGY

Highly Highly

Solubilitv Solubilitv

Swellable Swellable

NS. NS. EGLYCOL EGLYCOL

Swellable Swellable

NS. NS.

Swellable Swellable

PROPYLEN PROPYLEN

NS NS

NS NS NS

NS. NS.

NS NS

NS. NS.

Swellable Swellable

WATER WATER

Swellable Swellable

Swellable Swellable Swellable

Swellable Swellable

Solubility Solubility

of of

a a

tril tril

of of

with with

of of

acid. acid.

acid acid

loni loni

MW MW

blocks blocks

with with

sucrose sucrose

ethers ethers

blocks blocks

covalently-

grouos grouos

bonded bonded

alternated alternated

available available

polymer polymer

MISTRY MISTRY High High

e e

sequence sequence hydrophilic hydrophilic

copolymer copolymer

Or Or acrylic acrylic

Polymer Polymer

acrylic acrylic

containing containing

Polymers Polymers

hydrophobic hydrophobic

Acrylic Acrylic

ally ally

carboxyvinyl carboxyvinyl

Polar Polar

polyacry polyacry

pentaerythritol pentaerythritol

not not

SOURCE/CHE SOURCE/CHE with with

crosslinked crosslinked

data data

A A

NI NI

Synthetic Synthetic

POLYMER POLYMER

CROSS-

ACRYLATES ACRYLATES

CARBOMER CARBOMER

17.ACRYLATES/A 17.ACRYLATES/A

NCOPOLYMER NCOPOLYMER CRYLONITROGE CRYLONITROGE

16.ACRYLATES/ 16.ACRYLATES/

15. 15.

CROSS CROSS

ACRYLATE ACRYLATE

CI0-30ALKYL CI0-30ALKYL

POLYMER POLYMER

14. 14.

/VA /VA

Synthetics Synthetics THICKENER-

200V 200V

Aerosi Aerosi

NAME NAME

and and

Huber/ Huber/

200 200

Giulini/Gilugel Giulini/Gilugel

Degussa/ Degussa/

I I

JM JM

Zeothix, Zeosyl Zeosyl Zeothix,

ADE ADE

SUPPLIER/TR SUPPLIER/TR

gwm, gwm,

gums gums

NIA NIA

Carbomers Carbomers

and and

Xanthan Xanthan

Cellulose Cellulose

SYNERGISM SYNERGISM

NIA NIA

ION ION

TOLERANCE TOLERANCE

PH PH

TY TY

NIA NIA

NIA NIA NIA

1-7.5 1-7.5

STABILI STABILI

NIA NIA

Clear Clear

SOLUTION SOLUTION

CLARITY CLARITY

OF OF

in in

build build

(via (via

wire wire

sweating sweating

products products

abrasivity abrasivity

NIA NIA

viscosity viscosity

network) network)

Viscosity, Viscosity,

Thixotrophy. Thixotrophy.

"chicken "chicken

RHEOLOGY RHEOLOGY

stick stick

Suspension Suspension

With With

Reduces Reduces

Good Good

Non-

in in

oils oils

Glycol) Glycol)

Soluble Soluble

Solubility Solubility

(Propylene (Propylene

Soluble Soluble

polar polar

Soluble Soluble

SOLVENT SOLVENT

Not Not

NIA NIA

ORGANIC ORGANIC

y y

Not Not

Soluble Soluble

Solubilit Solubilit

WATER WATER

acid acid

of of

or or

oxide oxide

tWo tWo

silica. silica.

silicon silicon

formed formed

layers layers

silicone silicone

platelet platelet

octahedral octahedral

available available

stearic stearic

bet. bet.

RY RY

and and

dioxide dioxide

phyllosilicate phyllosilicate

consisting consisting

hvdroxide hvdroxide

not not

aluminum aluminum

Hydrophobic Hydrophobic

Minerals Minerals

dioxide dioxide

layer layer

layered layered

complex complex

Pyrogenic Pyrogenic

21 21

magnesium magnesium

Synthetic Synthetic

tetrahedral tetrahedral

between between

alminum/magnesium alminum/magnesium

structure-

clays clays

SOURCE/CHEMIST SOURCE/CHEMIST

data data

A - A

Silica Silica

Inorganic Inorganic

NI NI

Gel) Gel)

Silica Silica

FUMED FUMED

SMECTITE SMECTITE

ALUMINUM ALUMINUM

HYDRATED HYDRATED

18. 18.

19 19

SILICA SILICA

21. 21.

STEARATE STEARATE

20. 20.

/MAGNESIUM /MAGNESIUM

HYDROXIDE HYDROXIDE

CLAYS CLAYS

and and

(Precipitated (Precipitated

lnorganics lnorganics

SILICA SILICA THICKENER-