Development ofUltrananocrystalline Diamond (UNCD) Coatings Presented by

Jeffrey Elam Argonne National Laboratory

Materials, Sensors & Automation, and Glass Project Review June 21-24, 2004 Arlington, Virginia

A U.S. Department of EnergyOffice of Science LaboratoryOperated by The University of Chicago

Office of Science U.S. Department of Energy

Project Summary

• Goal: - Use UNCD to achieve significant energy savings in IOF industries

- First application – SiC multipurpose mechanical pump seals • Challenge:

- Develop technology to take UNCD from laboratory to market application - Need to mass produce UNCD coated parts

• Benefits: - Improved wear resistance and corrosion resistance of UNCD coated parts - 20% energy savings of 236 trillion Btu by 2020 in pump applications primarily

due to reduced friction losses • FY05 Activities:

- Commission and optimize 11-inch IPLAS system (up from 6-inch system) - Demonstrate UNCD coating of multiple seals simultaneously

- Demonstrate benefits of UNCD coatings on gas seals

- Verify tribological benefits of UNCD coated seals

- Perform long-term pump tests Pioneering Science andTechnology

2

Project Participants – Laboratory-led project

• Argonne National Laboratory - Energy Systems:

- Jeff Elam, John Hryn (Project POC), Joe Libera - Energy Technology:

- Ali Erdemir, Andriy Kovalchenko - Materials Science:

- Orlando Auciello, John Carlisle, Dieter Gruen, Mike Pellin, Alex Zinovev

• Industry Partners: - Advanced Diamond Technologies, Inc. (ADT)

- Neil Kane (Industry POC) - John Crane, Inc. - IPLAS Innovative Plasma Systems - Morgan Advanced Ceramics - Northwestern University - University of Illinois at Chicago 3 Pioneering Science andTechnology

Barriers –

Pathways –

Critical Metrics

1) Uniform nucleation and growth of UNCD

1) smooth films 2) good adhesion

2) Scale – up UNCD deposition process

3) Limited seal testing facilities

4) Commercialization of UNCD technology

Understand plasma deposition and surface seeding requirements, UNCD characterization and testing

Commission 11-inch plasma system

Use industrial facilities and expand lab capabilities

Launch company (ADT)

Develop seeding protocol to produce uniform UNCD films (COMPLETED)

Multiple seals coated with UNCD simultaneously

Perform successful pilot test (data indicate energy savings)

Sign toll-processing agreement

Pioneering Science and Technology

4

Ultrananocrystalline Diamond (UNCD) Properties

3-5 nm

0.5 nm

200 nm

TEM

AFM

• Hardness - 97 GPa

• Elastic Modulus - 970 GPa

• Fracture Strength - 5 GPa

• Grain Size - 2 - 5 nm • RMS Roughness - 0.5 - 1 µ-inch • Friction Coefficient - 0.03

Pioneering Science andTechnology

5

UNCD for Multipurpose Mechanical Pump Seals

UNCD Coating

Pioneering Science and Technology • UNCD to reduce friction and eliminate wear

6

Technical Barrier #1: Uniform nucleation and growth of UNCD

• Seeding to achieve smooth UNCD films

• Seeding to achieve excellent adhesion ofUNCD to SiC Seal

Pioneering Science and Technology

7

UNCD – Example of Poor Seeding

Sample: Unseeded CVD SiC

• Low nucleation density – discontinuous coating

Pioneering Science and Technology

8

UNCD – Example of Excellent Seeding

Sample: Mechanically Seeded α-SiC

• High nucleation density - dense, continuous, smooth film

Pioneering Science and Technology

9

Simultaneous UNCD and Carbon Nanofiber (CNF) Growth

SEM and TEM Following UNCD Treatment

Iron

EDAX Elemental Analysis

Fe Kα 0.4%

Edax

Sig

nal

0 1000 2000 3000 4000 5000 6000 7000 8000

Energy (eV)

SEM, TEM shows CNF with iron particle catalyst

• Trace Fe Contamination Catalyzes CNF Growth Pioneering Science and Technology • Developed Screening Process for Iron

10

UNCD Coating of Smooth 2” OD α-SiC Seals5

JC94Before Coating 0

-5

-10

-15

SEM of Uncoated Seal

Hei

ght (

Mic

roin

ches

)

-20

-25

Ra=0.6±0.1 µinch -30

5

JC94After UNCD 0

-5

-10

-15

-20

-25

Ra=0.7±0.1 µinch -30

Pioneering Science and Technology • UNCD is smooth, no roughness change from UNCD coating

11

UNCD Coating of Rough 1” OD α-SiC Seals

SEM of Uncoated Seal

Hei

ght (

Mic

roin

ches

)

Before Coating 20

10

0

-10

-20

-30

-40

-50

Ra=8±1 µinch -60

0 0.02 0.04 0.06 0.08 0.1 0.12

Distance (Inches)

Pioneering Science and Technology • Rough initial surface for 1” seals

12

Roughness Measurements of Rough 1” OD Seals Following UNCD Coating

Ave

rage

Rou

ghne

ss (M

icro

inch

)

4

6

8

10

12

Before Coating

After UNCD

48 49 50 51 52 53 54

Seal Number

Pioneering Science and • No roughness change from UNCD Coatings Technology

13

Adhesion Measurements Using Fracture Analysis

1 2

3

Conformal UNCD coating over Fracture of UNCD-SiC interface observed after Seal face and beveled edge diamond saw cutting (1). However, fracture also

observed along SiC grains (2) and UNCD film (3)

Pioneering Science and • Strong adhesion of UNCD Coating to SiC Surface Technology

14

UNCD Coating of 5” Gas Seals

• Improved coating technology required for 5” gas seals

• Coating must preserve precisely engineered taper

UNCD

SiC

10 microns 10 microns

Outside Edge Inside Edge

• Segment of 5” seal was coated in existing small-area plasma system

Pioneering Science and Technology • UNCD Maintains Critical Tolerance Across Face of 5” Gas Seal

15

Technical Barrier #2: Scale – up UNCDdeposition process

IPLAS 11” Microwave Plasma CVD System

• First unit of its kind in the world

• Will enable batch-coating of multiple 2” seals

• Will enable coating of intact 5” seals

Pioneering Science and Technology • Work is underway to install and commission this system

16

Technical Barrier #3: Limited seal testing facilities

• Building Test Pump Loop at Argonne for Measuring Seal Friction and Wear

• Installed Surface Profiler at Argonne

• Friction and Wear Analysis at John Crane Testing Facilities

Pioneering Science and Technology

17

Hot Water Test of UNCD-Coated Seals at John Crane

• 2” OD Seal

• 100 Hours

• Very aggressive test of materials properties

• Mimics harsh conditions in chemical process pump

• 100 hour test simulates 2 years of extreme use

Pioneering Science andTechnology

18

Hot Water Test of UNCD-Coated Seals

Uncoated UNCD-Coated

graphite SiC

blistering wear debris No wear!

graphite SiC

0 0

0 Distance (inch) 0.3 0 0.3 19

Wea

r Dep

th

Pioneering Science and Technology • Failure of uncoated seal, no detectable wear for UNCD-coated seal

Friction Measurements of UNCD Coated 2” SiC SealLow Initial Roughness

Torq

ue Uncoated SiC Seal

UNCD coated SiC seal

• Significantly Reduced Friction for Smooth Seal Surface

Uncoated

UNCD

Face Load

Pioneering Science and Technology

20

Friction Measurements of UNCD Coated 1” SiC SealHigh Initial Roughness

JC48 Uncoated

Low RPM

Fric

tion

Coe

ffic

ient

Uncoated

UNCD

0 10 20 30 40 50

Time (Minutes)

• Marginally Reduced Friction for Rough Seal Surface Pioneering Science and Current Study: Effect of Roughness on UNCD Friction Technology

21

Technical Barrier #4: Commercialization of UNCD technology

Advanced Diamond

Technologies

• Advanced Diamond Technologies - Argonne-initiated start-up company

- Exclusive license in UNCD application - Company officially launched in 2003 - Business plan established - Toll processor for seal manufacturers

- Agreements in principle reached with partners

Pioneering Science and Technology

22

Future Work Leading to Commercialization

• FY05 - Understand effect of initial substrate roughness on UNCD friction - Commission and optimize 11-inch IPLAS system (up from 6-inch

system) - Demonstrate UNCD coating of multiple 2” seals simultaneously

- Demonstrate benefits of UNCD coatings on gas seals

- Verify tribological benefits of UNCD coated seals

- Perform long-term pump tests • FY06-07

- Pilot tests (field tests): 2" seals, 5" seals

- Automation of UNCD deposition process

• FY07 - Commercialization (sign toll-processing agreements)- Final report

Pioneering Science and Technology

23