Current ESA funded activities on Cr(VI) free conversion ... · future replacements for chromate -based conversion coatings”. ESA-NASA joint activity concerning. ISQ Frame Contract

ESA UNCLASSIFIED - For Official Use

Current ESA funded activities on Cr(VI) free conversion coatings and lead free items development and testing

L.Pigliaru/J.HokkaMaterials and Processes SectionMechanical DepartmentESA, [email protected]

04/06/2019

ESA UNCLASSIFIED - For Official Use Lucia Pigliaru | 16/10/2018 | Slide 2

Agenda of the Presentation

CrVI alternatives development• Status of the R&D funded program dealing with CrVI alternatives development and testing• REACH regulation does limit/restrict use of hexavalent chromium-> The Sunset date for chromium

trioxide was September 2017• An application for authorization has been submitted, space applications are covered by CTACSub, EC

decision is pending

Lead free electronics development (overview)

• ECHA RAC has been requested by EC DG EMPL in January 2019 to update the existing health-based bOEL(air) and biological limit value (blood) for lead and its compounds under the Chemical Agents Directive (CAD). RAC is expected to issue an opinion by the end of 2019 (latest by mid-2020).

• Status of the activities performed in the frame of Joint Working Group on Pb-Free transition

REACH


Programs currently running (CrVI alternatives development)

“Evaluation of alternative surface treatments and coating systems as future replacements for chromate-based conversion coatings”.

ESA-NASA joint activity concerning

ISQ Frame Contract

ECD Project I and II and “Environment friendly conversion

coating”

IRUCOAT4SPACE

“Evaluate the suitability and availability of alternative surface treatments to hexavalent chromium”

“Environmentally friendly corrosion protective hybrid coating as substitute of chromium based conversion coatings for space applications”

“3 R&D project for the development and space qualification of SurtecCC on various aluminum alloys and large parts”


ESA-NASA joint programMain achievements and current status


Test Campaign

Test campaign divided into 3 phases Each phase tested under variety of different corrosive environments Best performing treatment in each phase used for testing in subsequent phase Best pretreatment performers from pre-screening tested on all substrates Best pretreatment + primer performers from screening tested on AA2024-T3


Selected Surface Treatments


Surface Treatment Testing

• Tested at both ESA and NASA

• Success criteria• NSSZ test: after 168 hours of exposure there should be no more than 5 isolated

spots or pits, none larger than 784µm in diameter, per test specimen• Humidity test: same as above• Thermal cycles: according to ECSS


Surface Treatment ResultsSalt Spray • All surface treatments on 6000 and 7000 alloy series

performed well• None of the tested options met the minimum 168 hours requirement for the 2024-T8 alloy

Humidity Test• No signs of corrosion observed on any of the test

panels under 50°C/95% RH at 2200 hours of testing• METALAST TCP-HF showed signs of corrosion on 2024-

T8 alloy after temperature increase• MAPSIL SILICo reached max 3500 hours for 6000

series and 7075 alloys

Thermal Cycling• Cracking around or through “high element”

containing particulates on 2024-T8, 7075-T6 and 7075-T73 alloys

Alloy Surface treatment Salt Spray Humidity Thermal CyclingMAPSIL

METALASTSurTec 650 V

BonderiteMAPSIL


BonderiteMAPSIL


BonderiteMAPSIL


BonderiteMAPSIL


Bonderite

Failed/Pulled fron testing

7075-T73

Test

No CorrosionMedium Corrosion

2024-T3

2024-T8

6061-T6

7075-T6

Sheet1

Surface TreatmentTest

AlloyMAPSIL SILICo (thin)METALAST TCP-HFSurTec650 VBonderite M-NT 65000AlloySurface treatmentSalt SprayHumidityThermal Cycling

2024-T32500 hours2500 hours2500 hours2500 hours2024-T3MAPSIL

2024-T82500 hours


Surface Treatment Testing with Primer and test (2nd phase)

2024-T3 chosen due to its poor corrosion resistance, making it an ideal screening alloy


Surface Treatment selected for the 2nd phaseFollowing the previous phase of the test campaign, the following surface treatments were identified as possible replacements by NASA


Primers selected for the 2nd phase


Salt Spray Results

• MAPSIL SILICo AS primer performed excellent in combination with all surface treatment• NAVALCOAT primer also performed excellent in combination with all surface treatment (however primer showed blistering across panel)• All panels coated with NAVALCOAT primer appeared white over surface at 500 hours (after 1000 hours, panels once again appeared dark grey)• 16708TEP/16709CEH primer in combination with METALAST TCP-HF and Bonderite M-NT 65000 treatments showed good performance but poor performance with SurTec 650 V• 02GN084 and MAPSIL SILICo (thick) primers showed medium performance in combination with the different surface treatments• MAPSIL SILICo (thick) performed poorly on its own

Primers METALAST TCP-HF SurTec 650V Bonderite None16708TEP/16709CEH N/A

02GN084 N/ANAVALCOAT * * * N/A

MAPSIL SILICo (thick)MAPSIL SILICo AS N/A

Surface Treatments

*Some panels did show signs of blistering , not enough to qualify as a failure

Sheet1

Surface Treatment

AlloyMAPSIL SILICo (thin)METALAST TCP-HFSurTec650 VBonderite M-NT 65000

2024-T32500 hours2500 hours2500 hours2500 hours

2024-T82500 hours


Conclusions of the 1st and 2nd phases• Potential surface treatments alternatives for 6000 and 7000 series alloys identified• Additional testing needs to be done to identify alternative surface treatments for 2000 series alloys• MAPSIL SILICo (thin) and SurTec 650 V performed best as surface treatment on 6061 and 7075 alloys• SurTec 650 V however performed poorly when used in combination with primers• MAPSIL SILICo (thick) showed only medium performance when used in combination with primers and poorly on its own• MAPSIL SILICo AS showed excellent performance with all surface treatments• NAVALCOAT primer showed excellent performance with all surface treatments however requires further work to counter blistering• Potential candidates may have been identified to move onto phase 3 of the test campaign


Future Steps (3rd phase)

• Topcoat completed by MAP and samples delivered to ESTEC• Testing of best performing pretreatments with primers for topcoats • Exposure in Kourou test facility (additional rack under procurement to accommodate the large number of samples)

2 Topcoat system have been selected (applied on 2024 T3, 2219-T87 and 7075-T73 aluminium alloy):• E’ + MAP® AQ STATIC• MAPSIL® SILICO + E’ + MAP®

AQ STATIC


ECD ProgramMain achievements and current status


ECD I: Organization of the project• Prequalification phase: several destructive and reduced environmental test on chromated and painted test samples• Qualification phase: destructive and environmental test on qualification test samples and flight representative hardware


ECDI: Materials and surface treatment selected• Alloys selected:

• EN AW 6063 T651• EN AW 6082 T651• EN AW 7075 T7351

• All substrate have been treated with Surtec 650 RTU

• Flight representatives samples were used


Results of the pre-qualification campaign

• 6XXX series test samples survived all 168h NSS test regardless to coating mass• Several corrosion pretreatment were tested to increase the corrosion resistance of 7075 alloy that finally survived the 168h NSS test successfully

PU1 and SG121FD painting process parameters were optimized in house and successful results obtained after test


Results of the qualification campaign

• More than 80 samples together with flight representative hardware were investigated using visual inspection, dry/wet wipe test, microscopy, layer weight measurement, contact electrical resistance and tape lift test

• Test items were subjected to environmental test like bake out, humidity, thermal vacuum cycling and thermal cycling. NSST were also performed.

• All test have been passed successfully


ECDII (continuation of ECDI)Selected Alloys:• EN AW 1050 H0 sheet metal• EN AW 2024 T351• EN AW 2024 T851• EN AW 5052 H22• EN AW 6061 T651• EN AW 6061 T6 sheet metal• EN AW 6063 T651• EN AW 6082 T651• EN AW 6082 T6 sheet metal• EN AW 7075 T7351

Conversion coatings:• Surtec 650• Surtec 650 RTU• Surtec 650V

Topcoat:• MAP PUK (black paint)• MAP SG121FD (white paint)• MAP E‘ (primer)• LORD (Socomore)Aeroglaze Z306• LORD (Socomore)Aeroglaze 9741• LORD (Socomore) Aeroglaze 9947


ECDII (continuation of ECDI) – Test Program

• 1050 sheet metal + SURTEC 650 RTU• 2024 T351 + SURTEC 650V• 2024 T851 + SURTEC 650V• 2024 T851 + SURTEC 650• EN AW 5052 H22 + SURTEC 650 RTU• EN AW 5052 H22 + SURTEC 650 RTU + PUK• EN AW 5052 H22 + SURTEC 650 RTU + E’ + PUK• EN AW 6061 T651• EN AW 6061 T6 sheet metal• EN AW 6082 T651 + SURTEC 650 RTU (brush application)• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + PUK• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + E’ + PUK• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + SG121FD• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + E’ +

SG121FD• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + Z306• EN AW 6082 T651 + SURTEC 650 RTU (brush application) + 9741 +

Z306• EN AW 6082 T651 + 9947 + Z306• EN AW 6082 T6 sheet metal

150 samples!


ECDII (continuation of ECDI) – TCP results

Test Campaign PassedSuccessfully!


ECDII (continuation of ECDI) – TCP + topcoat results

Test Campaign PassedSuccessfully!


Environment friendly conversion coating development for large parts Technical objective is to develop a conversion coating process for large parts made of aluminum alloys using SURTEC650 chemical family. The process is based on spray and/or brush method instead of immersion to be able to treat large satellite parts like sandwich panels and adaptor rings.

Selected Alloys:• EN AW 5052 H22• EN AW 5005 H24• EN AW 6082 T651• EN AW 6082 sheet metal• EN AW 7075 T7351

Selected topcoat:MAP PU1MAP SG121FD Aeroglaze Z306.

Current Status:First Deliverable to be provided at the beginning of June


IRUCOAT4SPACE ProgramCurrent status


Main Objective and preliminary test program Hybrid Material Based on SiO2-ZrO2-Organic Interconnected Network Synthesized by sol-gel technique and dip-coating deposition (spraying in process) Protection on Zn-coated Steel (delay ofZn and Steel corrosion, aestheticmaintenance) Alkaline, wear and UV resistant Excellent matrix for incorporation of otherfunctional components: corrosion inhibitor,dyes, nanoparticles, conductive polymers Thickness range: 1.5 - 4 microns IRUCOAT patent application: EP16382471Dec 2016 and PCT/EP2017/076375 October2017


Main results – Salt Spray 168 h NSST

1 sample with 1 pit1 sample with 2 pits3 samples without pits

336 h NSST1 sample with 1 pit1 sample with 2 pits3 samples without pits

Requirement after 168 h NSST (MIL 5541)< 5 pits in one sample and < 15 pits in 5 samples

AA6061-T6 168 h NSST5 samples without pits

336 h NSST5 samples without pits

AA6063-T6

AA6082-T6

2 plates 5 x 3 inchassessed at 168h

168 h NSSTNo pits at naked eye

observation

5 plates 5 x 3 inchassessed at 168

and 336 h

5 plates 10 x 3 inchassessed at 168 and

336 h


Main results – thermal cycles and influence in thermo-optical properties

AA6063-T6 X Alodine 1200SX

Optical propertiesNot affected bythermal cycling(-70 to 100ºC, 100 cycles)

Reference Solar absorptance Infrared emittance

Before thermal cycling

After thermal cycling

Before thermal cycling

After thermal cycling

AA6063 T6 IRUCOAT 0.28 0.29 0.42 0.41

Alodine 1200S 0.40 0.43 0.80 0.70

AA6082 T6 IRUCOAT 0.39 0.40 0.51 0.52

Alodine 1200S 0.48 0.49 0.80 0.70

AA6082-T6

Thermal cycling (-70 to 100ºC, 100 cycles) + SST (168 hours)


Comparison of Cr6 conversion coatings and IrucoatConversion

coatingAluminum

alloy

Visual and microscopic

analysis

SST (336h)

Damp heat test (168h)

Thermal cycling

Thermal cycling +

SST (168h)

AA6082 T6 Isolated pits No visible changes No visible changesPitting

(>5 pits)


(>5 pits)


(>5 pits)

AA6063 T6 No corrosion No visible changes No visible changesPitting

(>5 pits)

AA6082 T6 Pitting (>5 pits) No visible changes No visible changesPitting

(>5 pits)


(>5 pits)

AA6082 T6 Darkening Grey spots Grey spots Pitting (>5 pits)

AA6063 T6 Darkening and grey spots Intense darkeningNo visible changes

Pitting (>5 pits)

AA6082 T6 Darkening Slight darkening Slight darkeningPitting

(>5 pits)

AA6063 T6 Slight darkening Slight darkening Slight darkeningPitting

(>5 pits)

AA6082 T6No pits observed with naked eyes

(168 h)

No visible changes (up to 840 h)

No visible changes

Pitting (>5 pits)

AA6063 T6 No corrosion No visible changes (up to 840 h)No visible changes No pitting

IRUCOAT

Powdery, peeling-off

Uniform, iridiscent

golden color

Homogeneous, very light grey

colour

Light grey colour

Light grey

Alodine 1200S

Surtec 650

Iridite NCP

TEC

BONDERITE M-NT 5700

Homogeneous glossy finish

• Excellent corrosion resistance comparable to Alodine 1200S (SST and damp heat test).

• Better corrosion resistance than Alodine 1200S in SST when panels were previously subjected to thermal cycling.

• Surface contact resistance in the range of MIL DTL 81706B requirements.

• Excellent solvent resistance.• Lower solar absorptance (higher

reflectance) and infrared emittance than Alodine 1200S. Values not affected by thermal cycling test.


Current Project (ESA funded) – Summary The main objective of this project is the optimization and scale-up of a protective coating (IRUCOAT) for aluminium alloys components of space devices, as a substitute of Cr-based products.

Project duration: 24 months

Basic characterization performed on AA2024


Current Project (ESA funded) – Status Modification of IRUCOAT formulation (in collaboration with external services)

Dry extract of IRUCOAT: 39,21% dilution with 1-methoxy-2-propanol and filtration 1µm Optimization of Spraying and Deep Coating parameters (2 series of samples) All samples were cured for 8h @ 120°C

Preliminary Results - Visually, the coating appears quite homogeneous, although further improvement in the spraying technique is needed

Series 1 : thickness around 3-3.3 µm Series 2: thickness around 3.5 µm


Current Project (ESA funded) – Status

10-2 10-1 100 101 102 103 104 105101

102

103

104

105

106

107

|| (

)

Frequency (Hz)

IS2_S1P6_0h_2019-04-24 IS2_S1P6_2h_2019-04-24 IS2_S1P6_5h_2019-04-24 IS2_S1P6_24h_2019-04-25

AA2024 Sprayed (Series 1)

10-2 10-1 100 101 102 103 104 105101

102

103

104

105

106

107

|Z| (Ω

cm

2 )

Frequency (Hz)

IS4_S2P5_0h_2019-04-24 IS4_S2P5_2h_2019-04-24 IS4_S2P5_5h_2019-04-24 IS4_S2P5_24h_2019-04-25

AA2024 Sprayed (Series 2)

10-2 10-1 100 101 102 103 104 105101

102

103

104

105

106

107

|Z| (Ω

cm

2 )Frequency (Hz)

IS13_BB3E_0h_2019-04-29 IS13_BB3E_2h_2019-04-29 IS13_BB3E_5h_2019-04-29 IS13_BB3E_24h_2019-04-30

AA2024 dip-coated

EIS of samples in 0.05 M NaCl

10-2 10-1 100 101 102 103 104 105101

102

103

104

105

106

107

|Z| (Ω

cm

2 )

Frequency (Hz)

IS2_S1P6_24h_2019-04-25 IS4_S2P5_24h_2019-04-25 IS13_BB3E_24h_2019-04-30

Comparison dip-coated vs. sprayed at 24h immersion in NaCl


Conclusion and next step• Several activities are running in parallel, not limited to ESA funding• Based on the results of the test campaigns some promising conversion treatments for specific

alloys have been identified• Qualification activities are held in parallel by Industry and some substrate/conversion coating

combinations are already qualified successfully for future mission• Based on the experience acquired from all the activities performed on this topic a guideline to

be used as baseline for project qualification has been issued from Materials and Processes section (ESA-TECMSP-TN-007384 Rev2.)

However some work remains still to be done concerning:• Most test activities are performed on lab scale and require industrialization

(challenge!)• The possibility to identify reliable treatment especially for demanding aluminum

alloys (e.g AA 2000 and 7000 series).• The verification of the new system reliability in combination with topcoat/paint and

bonding


Lead free electronics - Background• The European Space Sector can no longer avoid the need to plan and implement a managed transition to lead-free electronics. The stimulus comes from:

SubstanceCAS number(s)

CLP Annex VI (SVHC class.)

SIN List (ChemSec)

Candidate List(inclusion date)

ECHA Recommendation

Annex XIV Comments

Lead7439-92-1

Repr. 1A YES YES (27/06/2018)

NO, but ECHA draft recommendation may be expected in Sept 2019 for consultation (TBC by mid-June 2019 ”MSC-65”)

NO – No sunset date today: worst case could be in mid-late 2024

RoHS/EEE: Space-related exclusion from scope but commercial threat of obsolescence due to the abandon of lead in some other sectors


COTS Soldering

• Strong Emergence of the Low Earth Orbit (LEO) markets.

• New ways of assessing/ taking risks with Venture Capital and Public-Private Partnerships.

• Mass production concepts emerging.• Need to access fast the new technologies

with increased performance.• ESA COTS Steering Committee is working:

to issue a set of recommendations for the use of COTS in future Agency programmes/“new space” and a roadmap/ required next steps to achieve the above (Q2 2019).

Commercial Pressure

•What is the risk of supply chain disruption for leaded solders?

•Going to lead-free solders may negativelyaffect the management of Tin whiskers risk.

•Going to lead-free soldering is a two step process: First the necessary R&D leading to the choice

of the best candidates for Space Industry utilization. This R&D could be common and shared by all.

Second each company will have to qualify the new solder for each of their Assembly plants, a mammoth and costly undertaking.


Lead Free Working Group_Mandate• Gap analysis

o Substantial work has been performed by companies for commercial environments, but much less has been done for the extreme conditions encountered in space and other high-reliability applications (military, avionics, medical, etc.)

o Still today, very little long-term reliability data (more than 5 years) exist for lead-free electronics

• Roadmap and necessary activities o Credible planning with realistic budgets

• Lead-free transition planning for the European Space Industryo Reliability assessment and key reliability risks in lead-free electronics


Lead Free Transition planThe Lead Free Transition Plan will address the following topics:

a. Materials and EEE parts selection b. Supplier compliance and guidelines for procurement c. Changes in assembly processes d. Reliability assessment and key reliability risks in lead-free electronics

The first version of this roadmap and lead-free transition plan shall be presented no later than Q4/2019. For the second and third strategic goals, the working group should record the way forward in completing the Pb-free transition, including identifying the work being done elsewhere such as harmonization and non-space industry activities.

ESA UNCLASSIFIED - For Official Use

Thank you for attention

[email protected]@esa.int

Slide Number 1Agenda of the PresentationPrograms currently running (CrVI alternatives development) Slide Number 4Test Campaign Selected Surface TreatmentsSurface Treatment TestingSurface Treatment ResultsSurface Treatment Testing with Primer and test (2nd phase)Surface Treatment selected for the 2nd phasePrimers selected for the 2nd phaseSalt Spray ResultsConclusions of the 1st and 2nd phasesFuture Steps (3rd phase)Slide Number 15 ECD I: Organization of the projectECDI: Materials and surface treatment selectedResults of the pre-qualification campaignResults of the qualification campaignECDII (continuation of ECDI)ECDII (continuation of ECDI) – Test Program ECDII (continuation of ECDI) – TCP resultsECDII (continuation of ECDI) – TCP + topcoat resultsEnvironment friendly conversion coating development for large parts Slide Number 25Main Objective and preliminary test programMain results – Salt Spray Main results – thermal cycles and influence in thermo-optical propertiesComparison of Cr6 conversion coatings and IrucoatCurrent Project (ESA funded) – Summary Current Project (ESA funded) – Status Current Project (ESA funded) – Status Conclusion and next stepLead free electronics - BackgroundCommercial PressureLead Free Working Group_MandateLead Free Transition planThank you for attention

Documents

Current ESA funded activities on Cr(VI) free conversion ... · future replacements for chromate -based conversion coatings”. ESA-NASA joint activity concerning. ISQ Frame Contract