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

Non Skid Coating Formulation Utilizing a Design of Experiments (DOE)

Approach

TRFA Annual Meeting, Boston MA4 October 2004

Charles S. TricouApplied Research Laboratory

The Pennsylvania State University

Repair and Replacement

• Repair is time-, material-, and labor-intensive.

• Repair costs Range from $13- $25 /ft2

– CV 63 (November 2000)» 116,000 ft2

» Labor: $22.50 / ft2

» Material: $ 2.80 / ft2

– CVN 72 (April 2004)» 70,000 ft2

» Cost: $1.4 Million ($20 / ft2 )

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

• 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

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.

Performance Measurements (Outputs)

Coating performance measurements Adhesion

Corrosion (QUV, Salt Fog, Immersion, etc.)

Service-specific durability tests• Erosion

• Impact Resistance

• Chemical Resistance

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

DOE – How it Works2-Factor (full factorial) Linear

Linear Design 2 levels for each factor 2n trials

For 2 factors n = 2

Factor 1

Fac

tor

2

Provides information about interactions

2-Factor (full factorial) Quadratic

Factor 1

Fac

tor

2

Non-Linear Design 3 levels for each factor 3n trials

For 2 factors n = 2

3-Factor (full factorial) Linear

Factor 1

Factor 2Linear Design 2 levels for each factor 2n trials

For 3 factors n = 3

Factor 3

Mixture Designs

Constraints C1 + C2 + C3 = Fixed % Component 1

Component 3Component 2

Binary Blend

Non Skid FormulationComponents & 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

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.

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.

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)

D-Optimal Design: 38 Total Trials Run

Curing Agent 1

MOD 1 MOD 2 MOD 3 AP 1 AP 2

1 0.00 0.0 15 0 0.5 02 1.00 0.0 30 0 0 0.53 1.00 0.0 0 0 0.5 04 1.00 0.0 30 0 0.25 05 0.00 0.0 0 30 0 0.56 0.50 0.0 0 0 0 0.57 0.00 0.0 30 0 0.5 0.58 1.00 30.0 0 0 0 09 0.00 30.0 0 0 0.5 0.2510 0.00 0.0 0 0 0 011 1.00 0.0 0 30 0 0.2512 0.00 0.0 15 15 0 013 0.25 3.8 3.75 18.75 0.25 0.12514 0.00 0.0 0 30 0.5 015 0.00 0.0 0 0 0 016 1.00 0.0 15 0 0 017 1.00 15.0 0 15 0.5 018 0.00 15.0 15 0 0.5 019 1.00 15.0 0 0 0.5 020 0.00 0.0 15 15 0 021 0.00 30.0 0 0 0 022 0.00 0.0 30 0 0 0.523 1.00 30.0 0 0 0.5 0.524 0.00 0.0 0 30 0.5 0.525 1.00 0.0 0 15 0 0.526 0.50 10.0 10 0 0.25 0.2527 1.00 0.0 0 0 0.5 028 1.00 0.0 0 0 0.25 0.529 0.00 0.0 0 0 0.5 0.530 1.00 0.0 30 0 0.5 0.2531 1.00 15.0 0 15 0 0.532 0.00 0.0 0 0 0.5 0.533 0.50 0.0 0 30 0 034 1.00 0.0 0 15 0 0.535 0.00 30.0 0 0 0 0.536 1.00 0.0 0 30 0.5 037 0.00 0.0 30 0 0 038 1.00 0.0 0 30 0.5 0.5

D-Optimal Design: 38 Total TrialsFirst 13 trials

RunCuring Agent 1

MOD 1 MOD 2 MOD 3 AP 1 AP 2

1 0.00 0.0 15 0 0.5 02 1.00 0.0 30 0 0 0.53 1.00 0.0 0 0 0.5 04 1.00 0.0 30 0 0.25 05 0.00 0.0 0 30 0 0.56 0.50 0.0 0 0 0 0.57 0.00 0.0 30 0 0.5 0.58 1.00 30.0 0 0 0 09 0.00 30.0 0 0 0.5 0.25

10 0.00 0.0 0 0 0 011 1.00 0.0 0 30 0 0.2512 0.00 0.0 15 15 0 013 0.25 3.8 3.75 18.75 0.25 0.125

Component Polyamine Curing Agent

1

Polyamine Curing Agent

2

MODIFIER 1

MODIFIER 2

MODIFIER 3

ADHESION PROMOTER

1

ADHESION PROMOTER

2

Resin (grams)

Total Mixture (grams)

Fraction of Available Epoxide Equivalents

0.00 1.00 0.00 15.00 0.00 0.50 0.00 100 200.00

Equivalents 0.00 0.44 0.00 0.06 0.00 0.0021 0.50 200.00grams 0.00 52.83 0.00 15.00 0.00 0.50 0.00 100 168.33

% Total 0.00 0.31 0.00 0.09 0.00 0.00 0.00 0.59 1.00

Conversions

Trial #1

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)

1 0.00 52.83 0.00 15.00 0.00 0.50 0.00 100.00 168.332 66.19 0.00 0.00 30.00 0.00 0.00 0.50 100.00 196.693 86.62 0.00 0.00 0.00 0.00 0.50 0.00 100.00 187.124 66.37 0.00 0.00 30.00 0.00 0.25 0.00 100.00 196.625 0.00 67.43 0.00 0.00 30.00 0.00 0.50 100.00 197.936 43.13 29.75 0.00 0.00 0.00 0.00 0.50 100.00 173.387 0.00 45.91 0.00 30.00 0.00 0.50 0.50 100.00 176.918 65.63 0.00 30.00 0.00 0.00 0.00 0.00 100.00 195.639 0.00 45.53 30.00 0.00 0.00 0.50 0.25 100.00 176.2810 0.00 59.50 0.00 0.00 0.00 0.00 0.00 100.00 159.5011 97.75 0.00 0.00 0.00 30.00 0.00 0.25 100.00 228.0012 0.00 56.55 0.00 15.00 15.00 0.00 0.00 100.00 186.5513 22.13 45.81 3.75 3.75 18.75 0.25 0.13 100.00 194.5714 0.00 67.69 0.00 0.00 30.00 0.50 0.00 100.00 198.1915 0.00 59.50 0.00 0.00 0.00 0.00 0.00 100.00 159.5016 76.22 0.00 0.00 15.00 0.00 0.00 0.00 100.00 191.2217 82.06 0.00 15.00 0.00 15.00 0.50 0.00 100.00 212.5618 0.00 45.72 15.00 15.00 0.00 0.50 0.00 100.00 176.2219 76.31 0.00 15.00 0.00 0.00 0.50 0.00 100.00 191.8120 0.00 56.55 0.00 15.00 15.00 0.00 0.00 100.00 186.5521 0.00 45.28 30.00 0.00 0.00 0.00 0.00 100.00 175.2822 0.00 45.66 0.00 30.00 0.00 0.00 0.50 100.00 176.1623 66.00 0.00 30.00 0.00 0.00 0.50 0.50 100.00 197.0024 0.00 67.69 0.00 0.00 30.00 0.50 0.50 100.00 198.6925 92.00 0.00 0.00 0.00 15.00 0.00 0.50 100.00 207.5026 36.44 25.14 10.00 10.00 0.00 0.25 0.25 100.00 182.0727 86.62 0.00 0.00 0.00 0.00 0.50 0.00 100.00 187.1228 86.43 0.00 0.00 0.00 0.00 0.25 0.50 100.00 187.1829 0.00 59.75 0.00 0.00 0.00 0.50 0.50 100.00 160.7530 66.56 0.00 0.00 30.00 0.00 0.50 0.25 100.00 197.3131 81.69 0.00 15.00 0.00 15.00 0.00 0.50 100.00 212.1932 0.00 59.75 0.00 0.00 0.00 0.50 0.50 100.00 160.7533 48.88 33.72 0.00 0.00 30.00 0.00 0.00 100.00 212.5934 92.00 0.00 0.00 0.00 15.00 0.00 0.50 100.00 207.5035 0.00 45.28 30.00 0.00 0.00 0.00 0.50 100.00 175.7836 98.12 0.00 0.00 0.00 30.00 0.50 0.00 100.00 228.6237 0.00 45.66 0.00 30.00 0.00 0.00 0.00 100.00 175.6638 98.12 0.00 0.00 0.00 30.00 0.50 0.50 100.00 229.12

D-Optimal Design: 38 Total TrialsFirst 13 trials

RunCuring 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)

1 0.00 52.83 0.00 15.00 0.00 0.50 0.00 100.00 168.332 66.19 0.00 0.00 30.00 0.00 0.00 0.50 100.00 196.693 86.62 0.00 0.00 0.00 0.00 0.50 0.00 100.00 187.124 66.37 0.00 0.00 30.00 0.00 0.25 0.00 100.00 196.625 0.00 67.43 0.00 0.00 30.00 0.00 0.50 100.00 197.936 43.13 29.75 0.00 0.00 0.00 0.00 0.50 100.00 173.387 0.00 45.91 0.00 30.00 0.00 0.50 0.50 100.00 176.918 65.63 0.00 30.00 0.00 0.00 0.00 0.00 100.00 195.639 0.00 45.53 30.00 0.00 0.00 0.50 0.25 100.00 176.2810 0.00 59.50 0.00 0.00 0.00 0.00 0.00 100.00 159.5011 97.75 0.00 0.00 0.00 30.00 0.00 0.25 100.00 228.0012 0.00 56.55 0.00 15.00 15.00 0.00 0.00 100.00 186.5513 22.13 45.81 3.75 3.75 18.75 0.25 0.13 100.00 194.57

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.

Team Participants

Applied Research LaboratoryEpoxy Chemicals, Inc.Advanced Systems Technologies, Inc. (AST)St. Gobain Mineral Abrasives