1. Non Skid Coating Formulation Utilizing a Design of Experiments (DOE) Approach TRFA Annual Meeting, Boston MA 4 October 2004 Charles S. Tricou Applied Research Laboratory The Pennsylvania State University

2. Repair and Replacement Repair is time-, material-, and labor- intensive. Repair costs Range from $13- $25 /ft 2 –CV 63 (November 2000) »116,000 ft 2 »Labor: $22.50 / ft 2 »Material:$ 2.80 / ft 2 –CVN 72 (April 2004) »70,000 ft 2 »Cost: $1.4 Million ($20 / ft 2 ) Durability Approximately 80% of CVN flight deck nonskid coatings are replaced following each deployment. Extending the durability and functionality of nonskid coatings to last through 2 full deployments will save the Navy ~ $5M per year. Nonskid coatings in arrested landing areas are removed and replaced 2 or 3 times per deployment cycle. Flight deck coatings have degraded during deployment to an extent necessitating repair. Repairs at foreign ports are very expensive and result in temporary loss of platform availability. Overview

3. Arrested Landing Area –Eliminate erosion of non-skid coating due to wire slap –Protect arresting cable from abrasion damage –Reduce or eliminate damage to nonskid coating from tail-hook impact Submarine Topside –Develop durable nonskid for continuous seawater immersion Future Research / Growth

4. Approach Develop a high-performance organic nonskid system Utilize multiple types of high-performance abrasives in conjunction with the development / refinement of modern epoxy and epoxy/urethane blends to achieve maximum nonskid functionality, strength, durability, chemical resistance and corrosion protection. Advanced epoxy blends and rapid-cure polymer technology State-of-the-art ceramic technology (material, shape, chemistry) A robust design of experiments approach will be used to identify the key parameters affecting all aspects of nonskid coating performance, and enable optimization of the nonskid system. This approach offers the potential of achieving maximum performance from an organic-based nonskid coating. After qualification, such a system may be used as a drop-in replacement for current epoxy-based systems.

5. Performance Measurements (Outputs) Coating performance measurements  Adhesion  Corrosion (QUV, Salt Fog, Immersion, etc.) Service-specific durability tests Erosion Impact Resistance Chemical Resistance

6. DOE Approach – What is it? Design of Experiments (DOE) is a scientific approach to experimentation. A good DOE will yield the following benefits:  Aid in the selection and isolation of the important variables to be studied  Minimize the number of experiments that must be carried out to yield meaningful results  Maximize the amount of information that can be extracted from the experiments  Minimize the cost of product development and process control

7. DOE – How it Works 2-Factor (full factorial) Linear Linear Design  2 levels for each factor  2 n trials  For 2 factors n = 2 Factor 1 Factor 2 Provides information about interactions

8. 2-Factor (full factorial) Quadratic Factor 1 Factor 2 Non-Linear Design  3 levels for each factor  3 n trials  For 2 factors n = 2

9. 3-Factor (full factorial) Linear Factor 1 Factor 2 Linear Design  2 levels for each factor  2 n trials  For 3 factors n = 3 Factor 3

10. Mixture Designs Constraints  C1 + C2 + C3 = Fixed % Component 1 Component 3Component 2 Binary Blend

11. Non Skid Formulation Components & Levels Components (Levels) A.Polyamine Curing Agent #1 (Stoich) B.Polyamine Curing Agent #2 (Stoich) C.Modifier #1 (0% – 30% by weigh of Resin) D.Modifier #2 (0% – 30% by weight of Resin) E.Modifier #3 (0% – 30% by weight of Resin) F.Adhesion Promoter #1 (0% – 0.5% by weight of Resin) G.Adhesion Promoter #2 (0% – 0.5% by weight of Resin) H.Base Resin (100 grams) Constraints: Total Modifier cannot exceed 30% 0 ≤ C + D + E ≤ 30 grams

12. Design Strategy Ideally, this design would have been performed utilizing a mixture design. However, this is exceptionally difficult to do using the commercial software available. In mixture design, the component ranges are defined according to weight contribution or volume contribution. In epoxy formulations, equivalent contributions can also be used. These contributions should be expressed as percentages of the total mixture. In this study, the constraints are such that it was not possible to create a mixture design utilizing the available software. Consequently, we opted to perform this formulation study in the manner of a factorial experiment.

13. Design Strategy In total, there are 8 potential components that may be used in the coating formulation. However, the amount of base resin used in each trial is held constant at 100 grams. Since the amount of resin does not vary, the base resin may be eliminated as a variable, reducing the number of variables to 7. The actual levels of the polyamine curing agents are determined by stoichiometry. Because of stoichiometric constraints, the amount of one curing agent used will depend upon the amount of the other curing agent used. By defining the amount of one of the curing agents as a fraction of the total curing agent used, the other curing agent is eliminated as a variable. This reduces the total number of variables from 7 to 6.

14. Design Strategy A quadratic D-Optimal design was chosen for this experiment. The D-Optimal design provides substantial information with a a minimum number of trials. Components (Levels) A.Polyamine Curing Agent #1 (Fraction of total curing agent used: 0 - 1) B.Polyamine Curing Agent #2 (Stoich, based on amount of PCA1) C.Modifier #1 (0% – 30% by weigh of Resin) D.Modifier #2 (0% – 30% by weight of Resin) E.Modifier #3 (0% – 30% by weight of Resin) F.Adhesion Promoter #1 (0% – 0.5% by weight of Resin) G.Adhesion Promoter #2 (0% – 0.5% by weight of Resin) H.Base Resin (100 grams)

15. D-Optimal Design: 38 Total Trials Run Curing Agent 1 MOD 1MOD 2MOD 3AP 1AP 2 10.00 0.01500.50 21.00 0.030000.5 31.00 0.0000.50 41.00 0.03000.250 50.00 0.003000.5 60.50 0.00000.5 70.00 0.03000.5 81.00 30.00000 90.00 30.0000.50.25 100.00 0.00000 111.00 0.003000.25 120.00 0.015 00 130.25 3.83.7518.750.250.125 140.00 0.00300.50 150.00 0.00000 161.00 0.015000 171.00 15.00150.50 180.00 15.01500.50 191.00 15.0000.50 200.00 0.015 00 210.00 30.00000 220.00 0.030000.5 231.00 30.0000.5 240.00 0.00300.5 251.00 0.001500.5 260.50 10.01000.25 271.00 0.0000.50 281.00 0.0000.250.5 290.00 0.0000.5 301.00 0.03000.50.25 311.00 15.001500.5 320.00 0.0000.5 330.50 0.003000 341.00 0.001500.5 350.00 30.00000.5 361.00 0.00300.50 370.00 0.030000 381.00 0.00300.5

16. D-Optimal Design: 38 Total Trials First 13 trials

17. Conversions Trial #1

18. Experimental Design Run Curing Agent 1 (grams) Curing Agent 2 (grams) MOD 1 (grams) MOD 2 (grams) MOD 3 (grams) AP 1 (grams) AP 2 (grams) Resin (grams) Total Mixture (grams) 10.0052.830.0015.000.000.500.00100.00168.33 266.190.00 30.000.00 0.50100.00196.69 386.620.00 0.500.00100.00187.12 466.370.00 30.000.000.250.00100.00196.62 50.0067.430.00 30.000.000.50100.00197.93 643.1329.750.00 0.50100.00173.38 70.0045.910.0030.000.000.50 100.00176.91 865.630.0030.000.00 100.00195.63 90.0045.5330.000.00 0.500.25100.00176.28 100.0059.500.00 100.00159.50 1197.750.00 30.000.000.25100.00228.00 120.0056.550.0015.00 0.00 100.00186.55 1322.1345.813.75 18.750.250.13100.00194.57 140.0067.690.00 30.000.500.00100.00198.19 150.0059.500.00 100.00159.50 1676.220.00 15.000.00 100.00191.22 1782.060.0015.000.0015.000.500.00100.00212.56 180.0045.7215.00 0.000.500.00100.00176.22 1976.310.0015.000.00 0.500.00100.00191.81 200.0056.550.0015.00 0.00 100.00186.55 210.0045.2830.000.00 100.00175.28 220.0045.660.0030.000.00 0.50100.00176.16 2366.000.0030.000.00 0.50 100.00197.00 240.0067.690.00 30.000.50 100.00198.69 2592.000.00 15.000.000.50100.00207.50 2636.4425.1410.00 0.000.25 100.00182.07 2786.620.00 0.500.00100.00187.12 2886.430.00 0.250.50100.00187.18 290.0059.750.00 0.50 100.00160.75 3066.560.00 30.000.000.500.25100.00197.31 3181.690.0015.000.0015.000.000.50100.00212.19 320.0059.750.00 0.50 100.00160.75 3348.8833.720.00 30.000.00 100.00212.59 3492.000.00 15.000.000.50100.00207.50 350.0045.2830.000.00 0.50100.00175.78 3698.120.00 30.000.500.00100.00228.62 370.0045.660.0030.000.00 100.00175.66 3898.120.00 30.000.50 100.00229.12

19. D-Optimal Design: 38 Total Trials First 13 trials

20. Expected Outcome Within the design space defined by these components and by the levels of these components, we expect to identify formulations having the maximum possible performance for each of the performance criteria that we plan to measure. Toughness / Impact resistance Adhesion Corrosion Chemical Resistance We expect to be able to model the effect on coating performance resulting from varying the concentration of these components. We expect to utilize this model to identify a coating formulation capable of meeting the project goals.

21. Team Participants Applied Research Laboratory Epoxy Chemicals, Inc. Advanced Systems Technologies, Inc. (AST) St. Gobain Mineral Abrasives