Crowd Control Ways to Reduce Dependence on TiO2

Crowd Control Ways to Reduce Dependence on TiO2

Crowd Control Ways to Reduce Dependence on TiO2 without Sacrificing Key Performance Properties Dave Fasano Linda Adamson Dow Coating Materials American Coatings Show May 7, 2012 Crowding of TiO2 Decrease in Scattering Efficiency Well known effect1,2 Increases with TiO2 use level TiO2 Particles are not well separated

1. F. Steig; J. of Coatings Tech.; 53; 680; pp 75-79; 1981 2. S. Fitzwater and J. Hook; J. of Coatings Tech.; 57; 721; pp 39-47; 1985 May 7, 2012 Crowding of TiO2 Decrease in Scattering Efficiency Well known effect1,2 Increases with TiO2 use level TiO2 Particles are not well separated 1. F. Steig; J. of Coatings Tech.; 53; 680; pp 75-79; 1981 2. S. Fitzwater and J. Hook; J. of Coatings Tech.; 57; 721; pp 39-47; 1985

May 7, 2012 Crowding of TiO2 Decrease in Scattering Efficiency Well known effect1,2 Increases with TiO2 use level TiO2 Particles are not well separated Increasing PVC 1. F. Steig; J. of Coatings Tech.; 53; 680; pp 75-79; 1981 2. S. Fitzwater and J. Hook; J. of Coatings Tech.; 57; 721; pp 39-47; 1985 May 7, 2012 Crowding of TiO2

Decrease in Scattering Efficiency Well known effect1,2 Increases with TiO2 use level TiO2 Particles are not well separated Increasing PVC 1. F. Steig; J. of Coatings Tech.; 53; 680; pp 75-79; 1981 2. S. Fitzwater and J. Hook; J. of Coatings Tech.; 57; 721; pp 39-47; 1985 May 7, 2012 TiO2 Crowds at High Use Levels 0

10 20 TiO2 ( PVC) 30 May 7, 2012 TiO2 Crowds at High Use Levels 0 10 20

TiO2 ( PVC) 30 May 7, 2012 Crowding Effect of Extenders and Latex Binders How Do Extenders Affect the Crowding of TiO2? Do small particle size extenders space TiO2? Do Latex Binder Particles Affect Crowding of TiO2? Effects studied in below CPVC Paints Above CPVC paints

Extenders, especially small particle, contribute to hiding via porosity, but decrease resistance properties May 7, 2012 Crowding Effect of Extenders Start With an all TiO2 Paint; 190 pounds; 16 PVC TiO2 use level remains constant in all paints Commercial Extender and Opaque Polymer; 15 PVC Particle Size: 0.4 to 12 um Calcium Carbonate: natural and precipitated Various Clay/Silicate: kaolin, calcined, delaminated, zeolite

Maintain 36% Volume Solids; Adjust Binder Level Total PVC increases: 16 and 31 PVC All paint are below CPVC May 7, 2012 Crowding Effect of Extenders May 7, 2012 Crowding Effect of Extenders May 7, 2012 A Random TiO2 Distribution

May 7, 2012 Becomes Less Random May 7, 2012 Becomes Less Random May 7, 2012 To Make Room for Extenders May 7, 2012 To Make Room for Extenders

May 7, 2012 Crowding Effect of Extenders May 7, 2012 A Random TiO2 Distribution May 7, 2012 Becomes Less Random May 7, 2012 Becomes Less Random

May 7, 2012 To Make Room for Extenders May 7, 2012 Crowding Effect of Extenders May 7, 2012 Crowding Effect of Extenders May 7, 2012 Crowding Effect of Extenders

Opaque Polymer is a Light Scattering Pigment May 7, 2012 Opaque Polymer A Light Scattering Pigment Difference in refractive index Optimum Scattering Size; about 0.3 um Refraction (Difference in Refractive Index)2 TiO2 > Air > Extender Difference in Refractive Index

Material Refractive Index Latex Polymer 1.50 - 1.55 TiO2 2.75 1.25 Air

1.00 0.50 Mineral Extenders 1.5 1.6 <0.1 May 7, 2012 Formulating with Extenders and Opaque Polymer Scattering and Hiding

Small particle size extenders Other Properties Favored by large particle size Low Sheen Resistance Exterior Durability May 7, 2012 Gloss Effect of Extenders and Opaque Polymer May 7, 2012 Abrasive Scrub Effect of Extenders and Opaque Polymer

May 7, 2012 Exterior Durability of Extenders 17 Year Old Exposure Series No Opaque Polymer 139 lbs Opaque Polymer No Opaque

Polymer 139 lbs Opaque Polymer 41% TiO2 Reduction 29% TiO2 Reduction Large Particle Size Extender Large and Small Particle Size Extender

May 7, 2012 Formulating with Extenders Minimal Crowding Good Gloss Small Good Durability Good Flatting Particle Size Poor Durability

Non-Flatting Large Highly Crowded Not for Gloss May 7, 2012 Formulating with Opaque Polymer Scattering Minimal Unique Properties Crowding Good Gloss Good

Particle Size Small Large Durability Non-Flatting May 7, 2012 Crowding Effect of Binders TiO2 (190 pounds); 6 PVC extender Commercial Latex Binders

Particle Size Range: 0.1 to 0.5 microns Composition Refractive index All Acrylic ~1.50 Vinylacetate/Acrylic ~1.50 Vinylacetate/Ethylene ~1.50 Styrene/Acrylic ~1.55 May 7, 2012 Crowding Effect of Binders May 7, 2012 Crowding Effect of Binders

May 7, 2012 Crowding Effect of Binders May 7, 2012 Scattering Efficiency Scattering is Dependent on the (Difference in Refractive Index)2 Material Refractive Index (approx.)

Difference in Refractive Index (TiO2 Binder) All Acrylic 1.50 1.25 Vinylacetate/Acrylic 1.50 1.25

Vinylacetate/Ethylene 1.50 1.25 Styrene/Acrylic 1.55 1.20 TiO2 2.75

May 7, 2012 Crowding Effect of Binders Increasing Particle Size Increases TiO2 Crowding Decreased scattering efficiency High Solids Latex Binders and Morphologies Formulation and manufacturing latitude Free water Adhesion and rheology Increasing Refractive Index Decreases scattering efficiency Not a Crowding Effect

May 7, 2012 Increase TiO2 Separation TiO2 Efficiency is Related to TiO2 Particle Separation Formulation effects tend to decrease separation Use level of TiO2 Larger size extender Larger size latex binder Particles distribute randomly and independently May 7, 2012 Increase TiO2 Separation TiO2 Efficiency is Related to TiO2

Particle Separation Formulation effects tend to decrease separation Use level of TiO2 Larger size extender Larger size latex binder Particles distribute randomly and independently What if the Distribution of TiO2 Could be Controlled? May 7, 2012 Increase TiO2 Separation Strong interaction between pre-composite polymer and TiO2 Improved TiO2 distribution Less crowding; Greater scattering efficiency

Pre-Composite Polymer TiO2 Composite May 7, 2012 Composite Formation and TiO2 Distribution SEM of Regular Paint Brighter spots indicate TiO2 is above the surface SEM of Composite Paint

More uniform distribution of TiO2 Covered with polymer May 7, 2012 Crowding Effect of Binders May 7, 2012 Wet Hiding is Best for Composite TiO2 May 7, 2012 Crowding Effect of Binders

Increasing Particle Size Increases TiO2 Crowding Decreased Scattering Efficiency High Solids Latex Binders and Morphologies Formulation and Manufacturing Latitude Adhesion and Rheology Increasing Refractive Index Decreases Scattering Efficiency

Not a Crowding Effect Composite Formation Reduces Crowding More Uniform Distribution of TiO2 Greater Separation of TiO2 Increased scattering efficiency: dry and wet May 7, 2012 Formulating for Reduced TiO2 May 7, 2012 Formulating for Reduced TiO2 Experimental

Knowledge-Based May 7, 2012 Formulating for Reduced TiO2 Experimental Trial and Error One variable studies Levels Design of Experiment Bench High Throughput3 Knowledge-Based Protocols Remove / Replace

Tools for Options Best Utilization 3. J. Mecca, D. Fasano, Q. Zhang, D. Cummins, J. Hook; Waterborne Symposium; 2012 May 7, 2012 Formulating for Reduced TiO2 Experimental Trial and Error One variable studies Levels Design of Experiment Bench High Throughput

Knowledge-Based Protocols Remove / Replace Tools for Options Best Utilization Power Speed May 7, 2012 Protocol Approach PVC ( BVC ) Raw Material Regular

TiO2 Paint Composite TiO2 Paint TiO2 17 14 Opaque Polymer 10 13

Nepheline Syenite 18 18 Calcined Clay 5 5 Total PVC 50

50 Pre-Composite Polymer - ( 31 ) Letdown Polymer ( 50 ) ( 19 ) Quality Exterior Flat

Pre-Composite Polymer and Opaque Polymer Remove 15% TiO2 Replace with opaque polymer [equal PVC] Add pre-composite polymer [1.4 x TiO2(dry weight)] Maintain PVC / VS May 7, 2012 Protocol Approach PVC ( BVC ) Raw Material

Regular TiO2 Paint Composite TiO2 Paint TiO2 17 14 Opaque Polymer 10

13 Total PVC 50 50 Pre-Composite Polymer - ( 31 ) 5.7 0.929

57.6 3/7 414 47% 99 control 5.9 0.936 58.2 5/6 493 53% 92 32 /gallon

From a earlier, but similar, series Performance Scattering (S/mil) Contrast Ratio Tint Strength (Y, LB) Gloss (60 / 85) Abrasive Scrub (cycles) Household Stain Removal Adhesion (gloss alkyd) Raw Material Savings May 7, 2012 Reformulation Tool

Software, Spreadsheets or Computations Designed based on experience and models Streamline reformulation process Powerful and Fast May 7, 2012 Reformulation Tool Example: Quality Flat Formulation Predicted Savings for Opaque Polymer; up to $0.70/gallon

TiO2 removal up to 100 pounds / 100 gallons Opaque polymer use Similar performance; Some loss of wet hide Savings 80 Savings (/gallon) 70 60 50 40 30 20 10

0 0 50 100 TiO2 150 200 250 Starting

May 7, 2012 Reformulation Tool Example: Quality Flat Formulation Predicted Savings for Opaque Polymer ; up to $0.70/gallon TiO2 removal up to 100 pounds / 100 gallons Opaque polymer use up to 150 pounds / 100 gallons Savings Similar performance; Some loss of wet hide

80 Pick an option Savings (/gallon) 70 60 50 75 pounds TiO2 40 30 20

60 /gallon 10 0 0 50 100 TiO2 150 200 250

Starting May 7, 2012 Summary Extender and Binder crowd TiO2 Crowding increases with particle size Lowering scattering efficiency Large particle size ingredients are appropriate for other required performance Extenders - gloss, durability and resistance Binder - solids content, free-water Opaque polymer and pre-composite polymer

offer ways to reduce TiO2 Scattering and TiO2 distribution and efficiency Reduce cost and maintain performance Tools can reduce reformulation time May 7, 2012 Disclaimer HANDLING PRECAUTIONS Before using any product mentioned herein, consult the products Material Safety Data Sheet (MSDS)/Safety Data Sheet (SDS) for details on product hazards, recommended handling precautions and product storage. PRODUCT STEWARDSHIP

Dow has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This concern is the basis for our product stewardship philosophy by which we assess the safety, health, and environmental information on our products and then take appropriate steps to protect employee and public health and our environment. The success of our product stewardship program rests with each and every individual involved with Dow products - from the initial concept and research, to manufacture, use, sale, disposal, and recycle of each product. CUSTOMER NOTICE Dow strongly encourages its customers to review both their manufacturing processes and their applications of Dow products from the standpoint of human health and environmental quality to ensure that Dow products are not used in ways for which they are not intended or tested. Dow personnel are available to

answer your questions and to provide reasonable technical support. Dow product literature, including safety data sheets, should be consulted prior to use of Dow products. Current safety data sheets are available from Dow. Notice: No freedom from infringement of any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether products and the information in this document are appropriate for Customer's use and for ensuring that Customer's workplace and disposal practices are in compliance with applicable laws and other government enactments. The product shown in this literature may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. Dow assumes no obligation or liability for the information in this document. References to Dow or the Company mean the Dow legal entity selling the products to Customer unless May 7, 2012

Thank you for your time David Fasano [email protected] Linda Adamson [email protected] Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow May 7, 2012

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