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AP2

Validation of Alternatives to
Aliphatic Isocyanate
Polyurethanes
Presented by :
Joseph Curran
NASA Corrosion Technology Labs
Kennedy Space Center, FL

AP2

National Aeronautics and Space


Administration (NASA) Headquarters
chartered the Acquisition Pollution
Prevention (AP2) Office to coordinate
agency activities affecting pollution
prevention issues identified during
system and component acquisition
and sustainment processes.

AP2

The primary objectives of the AP2 Office are:


Reduce or eliminate the use of hazardous
materials (HazMats) or hazardous processes
at manufacturing, remanufacturing, and
sustainment locations.
Avoid duplication of effort in actions required
to reduce or eliminate HazMats through joint
center cooperation and technology sharing.

AP2

NASA Corrosion Technology Laboratories


through the USTDC contract at Kennedy
Space Center is tasked to perform the
necessary screening, laboratory, and field
tests for this project as outlined in the Joint
Test Protocol.

KSC Beach Atmospheric Corrosion Test Site

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NASA Corrosion Technology Laboratory


MISSION:
To develop corrosion control and detection technologies.
To investigate, evaluate, & determine material behavior in
corrosive environments
To reduce the use of hazardous
materials
FACILITIES-CAPABILITIES:
Atmospheric exposure site
Electrochemistry lab
Seawater immersion system
Coatings application lab
Accelerated corrosion equipment
Website
(http://corrosion.ksc.nasa.gov)

AP2

Outline
Why replace aliphatic isocyanate polyurethanes?

Overview of validation procedures


Test Coupon Matrix
Coating Selection
Results of Tests
Conclusion
Future Studies
Acknowledgements

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Why replace aliphatic isocyanate polyurethanes?


Isocyanates are classified as potential human carcinogens
and are known to cause cancer in animals.
The Occupational Health & Safety Administration (OSHA)
states that the effects of isocyanate exposure include:
irritation of skin and mucous membranes
chest tightness
difficult breathing
Effects of overexposure:
occupational asthma
lung problems
irritation of the eyes, nose, throat, and skin.

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Overview of Validation Procedures


This JTP was created from
engineering, performance,
and operational impact
requirements defined by a
consensus of NASA and Air
Force Space Command
(AFSPC) participants and
contains the requirements
and tests necessary to
qualify coating alternatives
for Aliphatic Isocyanate
Polyurethane applications.

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Overview of Validation Procedures


Phase One Screening Tests
TEST

REFERENCE

Pot Life (Viscosity)

ASTM D1200

Ease of Application

ASTM E376

Surface Appearance

ASTM D523, D2244

Accelerated Storage Stability

ASTM D1849

Cure Time

ASTM D4752

Cleanability

MIL-PRF-8328D, -85285

X-Cut Adhesion

ASTM D3359

Tensile Adhesion

ASTM D4541

Knife Test

FED-STD-141

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Overview of Validation Procedures


Phase Two Laboratory Tests
TEST

REFERENCE

Removability

ASTM D1200

Repairability

ASTM E376

Abrasion Resistance
Gravelometer
Fungus Resistance
Accelerated Weathering
Filiform Resistance

ASTM D523, D2244


ASTM D1849
N/A
ASTM D4752
MIL-PRF-8328D, -85285

Mandrel Bend Flexibility

ASTM D3359

Marine Exposure Environment

ASTM D4541

Cyclic Corrosion Resistance

FED-STD-141

Hypergol Compatibility
LOX Compatibility

KSC MTB-175-88, NASA-STD-6001


NASA-STD-6001

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Overview of Validation Procedures


Field Evaluations
(To be performed at Stennis Space Center, MS)

TEST

REFERENCE

Ease of Application

Technician Evaluation

Surface Appearance

ASTM E523, D2244

Dry-To-Touch

Technician Evaluation

Rocket motor test


stand to be used for
test coating application

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Test Coupon Matrix per System


Size
Quantity Type
Alloy
4"x6"x .1875"
24
Composite A-36 steel
4"x6"x .1875"
45
Flat
A-36 steel
3"x6"x .1875"
6*
Flat
A-36 steel
4"x12"x.1875"
6
Flat
A-36 steel
4"x4"x .032"
6
Flat
1008 steel
3"x5"x .032"
12
Flat
1008 steel
3"x5"x .025"
6
Flat
3003 H14Aluminum**
.75" round
60
Flat Disc
304 Stainless Steel
4"x4"
15
Flat
Aluminum Foil
*40 for the control coating/ **one system only

Coating Selections

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Manufacturer Product

Carboline

Sherwin
Williams

Coating
Type

System

Use

Carbozinc 11HS (primer)


IO Zinc
Carboguard 893 (intermediate) Epoxy
Carboxane 2000 (top)
Siloxane

Test

IO Zinc
Carbozinc 11HS (primer)
Carboguard 893 (intermediate) Epoxy
Urethane
Carbothane 134 HB (top)

Control

Zinc Clad 11 WB (primer)


Polysiloxane XLE (top)

IO Zinc
Siloxane

Test

Zinc Clad 11 WB (primer)


Fast Clad HB (top)

IO Zinc
Acrylic

Test

Zinc Clad 11 WB (primer)


Sher-Cryl HPA (top)

IO Zinc
Acrylic

Test

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Coating Selections Cont.


Coating
Type

Syste
m

Use

Interzinc 22 (primer)
Interseal 670 HS (intermediate)
Interfine 979 (top)

IO Zinc
Epoxy
Siloxane

Test

Interzinc 22 (primer)
Interseal 670 HS (intermediate)
Interfine 878 (top)

IO Zinc
Epoxy
Siloxane

Test

Cathacote 304V (primer)


Devron 201 (intermediate)
Devathane 359 (top)

IO Zinc
Epoxy
Urethane

Control

AquaSurTech D45-20 (primer) WB


D45-AMS (top) WB
Coating
D45-AMS (clear coat) WB
Products

Urethane
Urethane
Urethane

Test

IO Zinc
Epoxy
Siloxane

10

Test

Manufacturer Product
International
Protective
Coatings

ICI Devoe
Coatings

Ameron
International

Dimecoat 9H (primer)
Amercoat 383 (intermediate)
PSX-1001 (top)

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Test Results
Pot Life

Pot life was determined using a procedure to determine the


viscosity increase of a mixed multi-component liquid coating
system at room temperature and heated (solvent-borne only)
over a specified time. Viscosity was measured, using Zahn
Cups, initially and at 30 minute intervals for a period of 4 hours
or until failure. Cup efflux times in seconds (T) was converted
to viscosity values (V) in centistokes (cks) using the following
equations* for each respective cup:
Cup 1: V= 1.59T (1070 T)
Cup 2: Not Used
Cup 3: V= 10.23T (575 T)
Cup 4: V= 15.13T (545 T)
Cup 5: V= 27.27T (540 T)
*Equations derived from NIST traceable standard viscous oils.

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Test Results
Pot Life

Viscosity of Heated Samples 35OC


Final 35oC
Initial 25oC
Zahn cup time viscosity cup time viscosity Time
Interval Sprayable
(sec)
(cks)
(sec)
(cks)
System Cup
1
5
48
1298
57
1545
4 hrs
yes
2*
4
32
475
115
1743
1.5 hrs
no
3
4
56
845
31
459
4 hrs
yes
4
Water-Based
5
Water-Based
6
4
30
428
66
990
4 hrs
yes
7
3
35
336
48
484
4 hrs
yes
8*
5
35
911
60
1627
2 hrs
no
9
Water-Based
10
3
28
260
14
102
4 hrs
yes
* control coatings

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Test Results
Pot Life
Viscosity of Room Temperature Samples 25OC

Final 25oC
Initial 25oC
Zahn cup time viscosity cup time viscosity Time
(sec)
(cks)
(sec)
(cks)
Interval Sprayable
System Cup
1
5
48
1298
79
2161
4 hrs
no
2*
4
32
475
108
1637
2.5 hrs
no
3
4
56
845
50
746
4 hrs
yes
4
4
60
899
76
1143
4 hrs
yes
5
4
46
684
56
838
4 hrs
yes
6
4
30
428
93
1394
4 hrs
yes
7
3
35
336
67
672
4 hrs
yes
8*
5
35
911
52
1394
4 hrs
yes
9
1
73
101
77
109
4 hrs
yes
10
3
28
260
28
102
4 hrs
yes
* control coatings

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Test Results
Application Criteria Evaluation

System
1
2
3
4
5
6
7
8
9
10

Wet Coat
Finish
Runs Bubbles Sags Hiding
Smooth
Gloss
>7 wet
no
>7 wet 1 coat
Smooth
Gloss
no
no
no 2 coat*
Smooth
Gloss
no
yes**
no
1 coat
Smooth
Gloss
no
yes**
no
1 coat
Smooth
Gloss
no
yes**
no
1 coat
Smooth
Gloss
no
no
no
1 coat
Smooth
Gloss
no
no
no
1 coat
Smooth
Gloss
no
no
no
1 coat
Smooth Semi-gloss >1 wet
no
>1 wet 2 coat*
Smooth
Gloss
no
no
no
1 coat
*thin film coating/ **due to spraying directly on zinc primer

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Test Results
Visual Surface Appearance

Coating
System
1
2
3
4
5
6
7
8
9
10

Unaided Eye
Smooth glossy finish with uniform color.
Slight orange peel, glossy finish with uniform color.
Smooth glossy finish with uniform color.
Smooth semi-gloss appearance with uniform color.
Smooth semi-gloss appearance with uniform color.
Slight orange peel, glossy finish with uniform color.
Slight orange peel, glossy finish with uniform color.
Smooth glossy finish with uniform color.
Smooth semi-gloss appearance with uniform color.
Smooth glossy finish with uniform color.

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Test Results
Visual Surface Appearance

Coating
System
1
2
3
4
5
6
7
8
9
10

10x Magnification
No defects or irregularities observed.
No defects or irregularities observed.
No defects or irregularities observed.
Small crater-like anomalies observed on surface.
Small crater-like anomalies observed on surface.
No defects or irregularities observed.
No defects or irregularities observed.
No defects or irregularities observed.
No defects or irregularities observed.
No defects or irregularities observed.

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Test Results

ASTM D1849 Standard Test Method for Package


Stability of Paint
This test evaluates any changes in consistency and certain
other properties that may take place when liquid coatings are
stored at a temperature above 32F. This test simulates some
of the effects of storage for 6 months to 1 year at 75 3.5F.
One quart samples were obtained from each coating system.
Each un-opened container was evaluated for any skinning,
corrosion on the interior of the can, odors of putrefaction,
rancidity, or souring. The samples were weighed and stored,
undisturbed for one-month at 125 2F, and re-evaluated.
Then the coatings were applied to test coupons by brush and
the finish was examined for grains, lumps, and/or streaks.

Test Results

AP2

ASTM D1849-95 Container Condition


and Coating Finish Ratings

10
8
6
4
2
0

None
Very Slight
Slight
Moderate
Considerable
Complete Failure

AP2

Test Results

ASTM D1849-95 Pre- and Post Oven Container


Condition Results
Coating
System
1
2
3
4
5
6
7
8
9
10

Weight
Pre
Post
1503.2 1501.8
1180.8 1180.8
1161.3 1161.3
1000.2 999.4
1199.5 1198.9
1207.7 1207.5
1217.8 1217.8
1185.8 1185.1
1162.3 1162.0
1110.2 1109.8

Skinning
Pre Post
10 10
10 8
10 10
10 10
10 8
10 8
10 8
10 8
10 6
10 10

Pressure
Pre Post
10 10
10 10
10 8
10 10
10 10
10 10
10 8
10 10
10 10
10 6

Corrosion
Pre Post
10 10
10 10
10 10
10 10
10 10
10 10
10 10
10 10
10 10
10 10

Odor
Pre Post
10 4
10 4
10 10
10 10
10 10
10 2
10 4
10 8
10 10
10 10

AP2

Test Results
ASTM D1849-95 Post-Oven
Brushed Coating Finish Results
Coating
Coating Appearance
System Grains Lumps Streaks
1
10
10
10
2
10
10
10
3
10
10
10
4
10
10
10
5
10
10
10
6
10
10
10
7
8
8
10
8
10
10
10
9
10
10
10
10
10
10
10

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Test Results
Cure Time Test
ASTM D4752 Resistance Ratings

This practice describes a solvent rub technique for


assessing the cure of an organic coating.
Rating

Remarks

No effect on surface; no coating on cloth.

Burnished appearance in rubbed area; slight amount of coating on cloth.

Some marring and apparent depression of the film.

Heavy marring; obvious depression in the film.

Heavy depression in the film but no penetration to the primer.

Penetration to the primer.

Test Results

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ASTM D4752 Solvent Rub Ratings


ASTM Rating
System Acetone MEK

# of
days

Film
Loss

2*

14

2.3 mils

14

2.5 mils

8*

10

14

2.9 mils

* control coating systems

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Test Results

(0)

(0)

(0)

(2)

(0)

(1)

(0)

(0)

(0)

(0)

(0)

(0)

System 4 Solvent Rub Test Photographs


(ratings)

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Test Results

(1)

(1)

(1)

(2)

(2)

(1)

(1)

(1)

(2)

(0)

(1)

(1)

System 5 Solvent Rub Test Photographs


(ratings)

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Test Results

(0)

(0)

(0)

(0)

(0)

(0)

(0)

(0)

(0)

(0)

(0)

(0)

System 10 Solvent Rub Test Photographs


(ratings)

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Test Results
Cleanability

This test evaluates the resistance of a topcoat to soil


adhesion and staining. Performed using MIL-PRF85285 (Coating: Polyurethane, Aircraft and Support
Equipment, issued 1988, revised 2002) section 4.6.13
as a guideline.
Cleaning Efficiency = [(C-B) / (A-B)] 100%.
Where:
A= initial L* value
B= soiled sample L* value
C= final cleaned L* value

Test Results

AP2

Cleanability
Test Results
Coating System

Cleaning Efficiency (%)

97

2*

97

97

37

99

98

8*

98

96

10

15
*control coatings

Test Results

AP2

Cleanability

SYS 1

SYS 2*

SYS 3

SYS 4

SYS 5

SYS 6

SYS 7

SYS 8*

SYS 9

SYS 10

*control coatings

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Test Results
Wet X-Cut Tape Adhesion

X-cut adhesion test were performed in


accordance with FED-STD-141 Method 6301.3,
Adhesion (Wet) Tape Test, and evaluated using
ASTM D 3359, Standard Test Methods for
Measuring Adhesion by Tape Test, approved
1995, revised 2002), Method A. Panels were
immersed in DI water for 24 hours, dried with a
cloth, and scribed with an X. Tape was applied
on the scribe and removed.

AP2

Test Results
Wet X-Cut Tape Adhesion
ASTM D3359-02 Scribe Ratings

5A
4A
3A
2A
1A
0A

No peeling or removal.
Trace peeling or removal along incisions or at their intersection.
Jagged removal along incisions up to 1.6 mm (1/16") on either side.
Jagged removal along most incisions up to 3.2 mm (1/8") on either side.
Removal from most of the area of the X under the tape.
Removal beyond the area of the X.

AP2

Test Results

Wet X-Cut Adhesion Tape Test Results


Coating ASTM
System Rating
1
3A
2
5A
3
2A
4
0A
5
4A
6
3A
7
5A
8
4A
9
5A
10
0A

Failure Mode
Scribe tool caused jagged edges along incision
No damage
Scribe tool caused jagged edges along incision
Coating was severly blistered and was removed
Trace peeling along incision
Scribe tool caused jagged edges along incision
Scribe tool caused jagged edges along incision
Scribe tool caused jagged edges along incision
No damage
Coating was removed between parrallel lines

Test Results

AP2

Wet X-Cut Adhesion Tape Test Results

Sys 1

Sys 2*

Sys 3

Sys 4

Sys 6

Sys 7

Sys 8*

Sys 9

*control coatings

Sys 5

Sys 10

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Test Results
ASTM D4541 Tensile Adhesion

ASTM D4541 test evaluates the pull-off adhesion


strength of a coating. The test determines either
the greatest perpendicular force (in tension) that a
surface area can bear before a plug of material is
detached. Failures are described as percentages
of adhesion or cohesion of coating system
interfaces.

Test Results

AP2

3-Coat
System

2-Coat
System
Dolly
Glue
Top Coat
Mid Coat
Primer
Substrate

Coating System Interfaces

Test Results

AP2

ASTM D4541 Pull-Off Adhesion Results


Tensile
Coating Adhesion
(psi)
System
1
1765
2
2100
3
2050
4
935
5
760
6
1830
7
1785
8
2180
9
2235
10
855

Failure Interface
Primer
10%C
85%C

100%C
99%C
40%C

Mid-Coat Top-Coat
90%A
10%A
2%A
n/a
100%A
n/a
100%A
n/a
100%C
1%A
50%C

Glue
3%A

10%A
100%A
100%A

A- adhesion failure C - cohesion failure

Test Results

AP2

Dolly Pull-Off Adhesion Photographs

SYS 1

SYS 2*

SYS 6

SYS 7

SYS 3

SYS 4

SYS 8*
*control coatings

SYS 9

SYS 5

SYS 10

AP2

Test Results
Knife Test

The purpose of this test is to evaluate the various


coatings for brittleness, toughness, and tendency to
ribbon by cutting narrow parallel lines in the coating
with a serviceable knife that has a sharp blade.
The test was performed in accordance with FEDSTD-141, Paint, Varnish, Lacquer and Related
Materials: Methods of Inspection, Sampling and
Testing, approved 2001, Method 6304.2.

Test Results

AP2

FED STD 141D Knife Test Results


Coating
System
1
2
3
4
5
6
7
8
9
10

Coating Condition
Some chipping on scribed lines/ no peeling
No chipping or peeling
Slight chipping/ no peeling
No chipping/ Slight peeling
No chipping or peeling
No chipping or peeling
No chipping or peeling
No chipping or peeling
No chipping or peeling
Several lines disbonded and peeled

Test Results

AP2

FED STD 141D Knife Test Photographs

SYS 1

SYS 2*

SYS 6

SYS 7

SYS 3

SYS 4

SYS 8*
*control coatings

SYS 9

SYS 5

SYS 10

Test Results
Summary

AP2

Coating Systems
Test

10

Pot Life (Heated)

Pot Life (Room Temp)

Ease of Application

Surface Appearance

Accelerated Storage

Cure Time

Cleanability

X-Cut Adhesion

Tensile Adhesion

Knife Test

C- Control B- Better S- Similar W- Worse

AP2

Conclusion
After review of the Phase One screening
tests, coating systems 1,4,5, and 10 are
being considered for elimination from the
Phase Two testing.

AP2

Future Studies

Abrasion
Filiform
Mandrel bend
Chip resistance
Fungus resistance
Accelerated weathering
Removability and Repair tests
Marine exposure
Cyclic Corrosion Resistance
Hypergol Compatibility
LOX Compatibility

AP2

Thank you
For more information contact:
NASA AP2 Office:
Kevin Andrews 321-867-8477
Pattie Lewis 321-867-9163
http://www.acqp2.nasa.gov/

NASA Corrosion Technology Laboratories:


Jerry Curran 321-867-9486
http://corrosion.ksc.nasa.gov/