Afton Chemical presents Back to the Basics: Fundamental Building Blocks of Grease Formulation

Back to the Basics: Fundamental Building Blocks of Grease Formulation Joe Kaperick

74th STLE Annual Meeting & Exhibition Nashville, TN May 23, 2019

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Blueprint Explore the fundamental performance areas for which grease additives are primarily used Common questions and assumptions Generated data with core grease additives commonly used for particular attributes Use straight lithium base grease for comparison Look at single additive response and common combinations

Is there a difference between primary and secondary ZDDPs? Is EP performance in a grease really “all about the sulfur”? Is all sulfur created equal?

Is there really such a thing as synergistic combinations of antioxidants?

What’s a good measure of high temperature performance?

Are all additive packages created equal? Does “one size fit all”?

Are all rust tests equal?

Start to explore some of these questions…

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Building Materials ID 1° ZDDP 2° ZDDP 1°/2° ZDDP SIB SO AO BPD ZDDP Pack 1 ZDDP Pack 2 S/P Pack 1 S/P Pack 2 S/P Pack 3 S/P Pack 4

Description

%Zn

%P

%S

%N

%B

Primary ZDDP Secondary ZDDP Mixed ZDDP Sulfurized Isobutylene Sulfurized Olefin Phenolic/Aminic AO Mix Boron-Phos Dispersant Core ZDDP/Sulfur ZDDP/Sulfur + AO/RI Core S/P Core S/P + AO Core S/P Core S/P

9 9 9.2 4 2 -

8 8.2 8.4 0.7 3.5 1.8 1.2 0.8 1.3 1.2

16.7 17.1 17.8 46 12 22.9 12.1 36.1 25.6 29.6 32.5

1.2 1.7 0.1 0.6 0.8 0.9 0.8 1.1

1.0 -

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The Tools Test

ASTM

Worked 60 Penetration - 1/2 worker (mm/10)

D1403

Dropping Point, °C

D 2265

Standard bearing corrosion, DI (48 and 67 hr), % Rust

D1743 (mod)

EMCOR (DI and 100% SSW), Rating

D6138

Copper corrosion, (24 hrs @ 80°C, 100°C, 120°C), rating

D4048 (mod)

Pressure Vessel Oxidation Test (100 hr @ 99°C), psi loss

D942

Pressurized Differential Scanning Calorimetry (155 °C, 500 psi, O2), OIT, min

D5483

Thermogravimetric Analysis (temperature sweep to 900°C, under N2 atmosphere)

D6370

Rheology (temperature sweep from 40 - 250°C, tan delta) 4 Ball EP, Weld Point, kg

D 2596

4 Ball Wear (40kg, 75°C, 1200 rpm, 1 hr), mm

D 2266

Fafnir Fretting wear, mg

D4170

High Frequency Reciprocating Rig (4N, 20Hz, 1mm, on steel), COF @ 30°C - 130°C

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ZDDP ID

Alcohol chain

Alcohol type

%Zn

%P

%S

1° ZDDP

C4/C5/C8

Primary

9

8

16.7

2° ZDDP

C3/C6

Secondary Primary /Secondary

9

8.2

17.1

9.2

8.4

17.8

1°/2° ZDDP

C3/C4/C8

Component Base Grease

100 1° ZDDP 2° ZDDP 1°/2° ZDDP SIB

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

2° ZDDP + SIB

1°/2° ZDDP + SIB

99.20

99.22

99.23

98.60

98.62

98.63

0.80

0.80 0.78

0.78 0.77

0.77 0.60

0.60

0.60

Treat rates used to deliver equal phos (640 ppm)

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ZDDP – Oxidation

Test ASTM Pressure vessel oxidation (100 hr @ D942 99°C), psi loss

Base Grease 6.1 5.6

1° ZDDP 2° ZDDP 3.6

2.7

1°/2° ZDDP 2.5

1° ZDDP 2° ZDDP + SIB + SIB 3.1

7

ZDDP helps as secondary antioxidant.

Difficult to determine differences between types or effect of SIB.

Pressure Loss, psi

6 5 4 3 2 1 0 Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

2° ZDDP + SIB

1°/2° ZDDP + SIB

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3.8

1°/2° ZDDP + SIB 3.9

ZDDP – Oxidation

Test PDSC(155 °C, 500 psi, O2), OIT, min

200 180 160

ASTM D5483

Base Grease 41.5

1° ZDDP 2° ZDDP 126

203

1°/2° ZDDP 178

1° ZDDP 2° ZDDP + SIB + SIB 155

2⁰ ZDDP appears to be better AO, although SIB seems to flatten response.

OIT, min

140 120 100 80 60 40 20 0 Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

2° ZDDP + SIB

1°/2° ZDDP + SIB

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162

1°/2° ZDDP + SIB 183

TGA repeatability

0

Repeatability is decent and shows differentiation from base grease

-5

-10

-15

-20 50

150

250

350

450 550 Temperature, °C Base Grease

B-1

650

750

B-2

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850

ZDDP - TGA

0

ZDDP shows some increase in thermal stability of base grease

-5

-10

-15

-20 50

150

250

350

Base Grease

450 550 Temperature, °C 1° ZDDP (2)

2° ZDDP

650

750

1°/2° ZDDP

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850

ZDDP - TGA

0

-5

Addition of SIB shows some decrease in ZDDP effect -10

-15

-20 50

150

250

Base Grease

350

450 550 Temperature, °C

1° ZDDP + SIB

2° ZDDP + SIB

650

750

1°/2° ZDDP + SIB

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850

ZDDP – Rheology

Oscillatory Motion

Test Oil/Grease

Temperature Control

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ZDDP – Rheology

Oscillatory Motion

Test Oil/Grease

1

0.9

Tan Delta is ratio of G”/G’. Lower value is more “solid” while higher value is more “liquid”

Base Grease – repeat runs to show precision

0.8 0.7

Temperature Control

Dropping Point is 205⁰C

Tan Delta

0.6

Increase temperature at steady rate from 40⁰C to 250⁰C

0.5 0.4 0.3

Scatter of data likely due to liquification of grease and loss of contact between plates

0.2 0.1 0

40

Temperature, C

90

140 Base Grease

190

240

Base Grease (2)

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ZDDP – Rheology 1 0.9

See “break” at about dropping point temp but maintain structure up to 250⁰C

0.8 0.7

Tan Delta

0.6 0.5

Noise in data – instrument issue or larger thickener particles

0.4 0.3

0.2 0.1 0

40

Temperature, C Base Grease

90

140 Base Grease (2)

190 1° ZDDP

2° ZDDP

240 1°/2° ZDDP

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ZDDP – Rheology 1 0.9 0.8 0.7

Adding SIB appears to lower “liquification” of grease at dropping point

Tan Delta

0.6 0.5 0.4 0.3

0.2 0.1 0

40

Temperature, C 1° ZDDP

90

2° ZDDP

140 1°/2° ZDDP

1° ZDDP + SIB

190 2° ZDDP + SIB

240 1°/2° ZDDP + SIB

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ZDDP – Rheology 1 0.9 0.8

Is performance enhanced by smoother profile (less change in structural stability)?

0.7

Tan Delta

0.6 0.5 0.4 0.3

0.2 0.1 0

190

195 200 Temperature, C 1° ZDDP 2° ZDDP

205

210

1°/2° ZDDP

215 1° ZDDP + SIB

220

225 2° ZDDP + SIB

230

235

1°/2° ZDDP + SIB

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240

ZDDP – Extreme Pressure/Antiwear Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

D 2596

180

200

200

230

240

240

270

4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm D 2266

0.67

0.53

0.47

0.51

0.49

0.50

0.48

ASTM

4 Ball EP, Weld Point, kg

290 270

2° ZDDP 1°/2° ZDDP + SIB + SIB

0.8

ZDDP brings increase in EP protection and reduction in wear.

0.75 0.7

Weld Load, kg

250

0.65 230 0.6 210 0.55 190

0.5

170

0.45

150

0.4 Base

1° ZDDP Weld

Weld (+ Sulfur)

2° ZDDP Wear

1°/2° ZDDP Wear (+Sulfur)

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Wear Scar, mm

Test

ZDDP – Extreme Pressure/Antiwear Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

D 2596

180

200

200

230

240

240

270

4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm D 2266

0.67

0.53

0.47

0.51

0.49

0.50

0.48

ASTM

4 Ball EP, Weld Point, kg

290

2° ZDDP 1°/2° ZDDP + SIB + SIB

0.8

Mixed ZDDP appears to bring 30 kg additional weld protection.

270

0.75 0.7

Weld Load, kg

250

0.65 230 0.6 210 0.55 190

0.5

170

0.45

150

0.4 Base

1° ZDDP Weld

Weld (+ Sulfur)

2° ZDDP Wear

1°/2° ZDDP Wear (+Sulfur)

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Wear Scar, mm

Test

ZDDP – Extreme Pressure/Antiwear Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

D 2596

180

200

200

230

240

240

270

4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm D 2266

0.67

0.53

0.47

0.51

0.49

0.50

0.48

ASTM

4 Ball EP, Weld Point, kg

290

2° ZDDP 1°/2° ZDDP + SIB + SIB

0.8

No differences between ZDDP types for wear protection.

270

0.75 0.7

Weld Load, kg

250

0.65 230 0.6 210 0.55 190

0.5

170

0.45

150

0.4 Base

1° ZDDP Weld

Weld (+ Sulfur)

2° ZDDP Wear

1°/2° ZDDP Wear (+Sulfur)

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Wear Scar, mm

Test

ZDDP – Fretting wear Test

ASTM

Fretting wear, mg

D4170

Base Grease

27.8 33.6

1° ZDDP

28.3

2° ZDDP 1°/2° ZDDP

29.2

23.3 24.3

1° ZDDP + SIB

25.3 31.2

2° ZDDP 1°/2° ZDDP + SIB + SIB

30.7

1°/2° ZDDP may form better tribolayer under lower temp fretting conditions

34 32

Fretting wear, mg

30 28 26 24 22 20

Base Grease

1° ZDDP

2° ZDDP

1°/2° ZDDP

1° ZDDP + SIB

2° ZDDP + SIB

1°/2° ZDDP + SIB

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27.2 27.7

ZDDP – Friction (HFRR) 0.16

1° ZDDP gives thinner, smoother tribolayer (w/lower COF) while 1°/2° and 2° ZDDP give thicker, rougher layer

Coefficient of Friction

0.15

0.14

0.13

0.12

0.11 30°C

50°C

70°C

90°C

110°C

130°C

0.1

Base Grease A

1° ZDDP

2° ZDDP

1°/2° ZDDP

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Addition of SIB results in more noise possibly from surface competition between sulfur and ZDDP to form tribofilm.

ZDDP – Friction 0.16

Coefficient of Friction

0.15

0.14

0.13

0.12

0.11 30°C

50°C

70°C

90°C

110°C

130°C

0.1

Base Grease A

1° ZDDP + SIB

2° ZDDP + SIB

1°/2° ZDDP + SIB

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Sulfur Component

ID

% Sulfur

% Active Sulfur

Sulfurized Isobutylene

SIB

46

32

Sulfurized Olefin

SO

12

2

SIB SO 1° ZDDP

Base Grease

SIB

SO

100

99.20

99.22

0.60

SIB + 1° ZDDP SO + 1° ZDDP

99.23

98.60

0.6 2.19

2.19 0.80

0.80

Treat rates used to deliver equal sulfur levels (~2780 ppm) Activity of sulfur should be critical to EP, corrosion and other properties Interested in interaction with ZDDP due to common use of combinations Confidential and Proprietary - not to be copied, shared,shared, or reproduced in any media the express written permission of AftonofChemical Corporation.

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Sulfur - Corrosion Test Standard bearing corrosion, DI, % Rust

ASTM D1743

Ave % rust Standard bearing corrosion, DI, 67 hrs, % Rust

Base Grease

SIB

SO

SIB + 1° ZDDP

SO + 1° ZDDP

1° ZDDP

5/15/15

0/0/0

0/0/0

Dot/1/15

Dot/1/5

0/0/0

11.7

0

0

5.5

2.2

0

15/15/15

0/5/5

5/15/25

15/15/25

dot/dot/dot

15.0

3.3

15.0

21.7

0.5

1/2

1/2

2/2

2/3

2/2

D1743 mod

Ave % rust Emcor (DI Water), Rating

D6138

2/2

Both sulfur sources improve corrosion protection over base grease Iron sulfide protection?

ZDDP also reduces corrosion by itself Severity differences seen between tests In presence of ZDDP, both sulfur sources are less effective Suggests interaction between sulfur and ZDDP

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Sulfur - Corrosion Base Grease

SIB

SO

SIB + 1° ZDDP

SO + 1° ZDDP

SIB + 2° ZDDP

SIB + 1°/2° ZDDP

Copper corrosion, 80C, 24 hrs D4048

3a

2c

1b

1b

1b

1b

2a

Copper corrosion, 100C, 24 hrs D4048

3a

2c

1b

1b

1b

2a

2a

Copper corrosion, 120C, 24 hrs D4048

3a

2c

1b

1b

1b

2b

2a

Test

ASTM

As expected, higher activity sulfur in SIB causes copper corrosion Addition of 1° ZDDP helps protect copper Is ZDDP tying up active sulfur?

1°/2° ZDDP not as helpful Temperature only appears to impact 2° ZDDP – interaction with SIB? • P-NMR and testing in oil being carried out

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Sulfur - Oxidation Test

ASTM

Pressure vessel oxidation (100 hr @ 99°C), psi loss

D942

7

Base Grease 6.1 5.6

SIB 5.3

SO 2.4

SIB + 1° ZDDP 3.1

- SIB no apparent help as AO - SO and ZDDP both show reduction in oxidation

6

Pressure Loss, psi

5 4 3 2 1

0 Base Grease

SIB

SO

SIB + 1° ZDDP

SO + 1° ZDDP

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SO + 1° ZDDP 3.3

Sulfur - Oxidation Test

ASTM

PDSC(155 °C, 500 psi, O2), OIT, D5483 min

180 160

Base Grease

SIB

41.5

54.3

SO

SIB + 1° ZDDP

SO + 1° ZDDP

106

155

179

- SIB very slight effect as AO - SO has much more effect with 2 x OIT - ZDDP improves both (3 x OIT)

140

OIT, min

120 100 80 60 40 20 0

Base Grease

SIB

SO

1° ZDDP + SIB

SO + ZDDP

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Sulfur – Extreme Pressure/Antiwear Test

ASTM

Base Grease

SIB

SO

SIB SO + 1° ZDDP + 1° ZDDP

4 Ball EP, Weld Point, kg

D 2596

180

230

210

240

230

4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm

D 2266

0.67

0.91

0.97

0.49

0.50

270

Weld Load, kg

250

1

SIB gives better EP protection than SO but both sulfur sources cause increase in wear

0.9 0.8

230 0.7 210 0.6

190 170

0.5

150

0.4 Base Grease Sulfur alone

SIB + 1° ZDDP

SO Sulfur alone

+ 1° ZDDP

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Wear scar, mm

290

Sulfur – Extreme Pressure/Antiwear Test

ASTM

Base Grease

SIB

SO

SIB SO + 1° ZDDP + 1° ZDDP

4 Ball EP, Weld Point, kg

D 2596

180

230

210

240

230

4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm

D 2266

0.67

0.91

0.97

0.49

0.50

290

Weld Load, kg

250

Addition of ZDDP reduces wear and levels EP response of sulfur.

0.9 0.8

230 0.7 210 0.6

190 170

0.5

150

0.4 Base Grease Sulfur alone

SIB + 1° ZDDP

SO Sulfur alone

+ 1° ZDDP

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Wear scar, mm

270

1

AO/Borates Component Phenolic/Aminic AO Mix Boronated Phosphorylated Dispersant

1° ZDDP AO BPD

ID

%N

%B

%P

AO

1.2

-

-

BPD

1.7

1.0

0.7

Base Grease

1° ZDDP

1° ZDDP + AO

1° ZDDP + AO + BPD (1.5%)

1° ZDDP + AO + BPD (3%)

100

99.20

99.22

99.23

98.60

0.8

0.8

0.8

0.8

1.0

1.0

1.0

1.5

3.0

Used lower amount of AO to see interactions BPD levels used to reflect commonly used treats for dropping point enhancers Not all testing completed with 3% BPD

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AO/Borates – Physical properties

1° ZDDP

1° ZDDP + AO

1° ZDDP + AO 1° ZDDP + AO + BPD (1.5%) + BPD (3%)

Testing: Worked 60 Penetration - 1/2 worker (mm/10)

ASTM

Base Grease

D1403

233

239

239

238

237

Dropping Point

D 2265

205

205

209

239

288

Slight softening of grease AO has little effect on DP Borate shows expected increase in DP with treat rate

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AO/Borates - Corrosion

Testing:

ASTM

Base Grease

Emcor (DI Water), Rating

D6138

2/2

1° ZDDP

2/2

1° ZDDP + AO

1° ZDDP + AO 1° ZDDP + AO + BPD (1.5%) + BPD (3%)

1/0

Boronated dispersant appears to help with EMCOR rust protection

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0/0

AO/Borates - TGA

0

-5

BPD significantly increases thermal stability of grease structure

-10

-15

-20 50

150

250

350

450

550

Base Grease

1° ZDDP

1° ZDDP + AO + BPD (1.5%)

1° ZDDP + AO + BPD (1.5%)

650

750

1° ZDDP + AO

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850

AO/Borates - Rheology 1 0.9

BPD helps maintain more consistent grease structure through the dropping point temp.

0.8

Tan Delta

0.7 0.6 0.5 0.4 0.3 0.2

0.1 0 40

Temperature, °C

1° ZDDP

90 ZDDP + AO

140 ZDDP + AO

190

240

ZDDP + AO + BPD (1.5%)

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AO/Borates - Rheology

1

Higher treat of BPD may help keep liquid nature at higher temperature but need additional testing for comparison.

0.9 0.8

Tan Delta

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 40

Temperature, ⁰C

90 1° ZDDP

140 ZDDP + AO

190 ZDDP + AO + BPD (1.5%)

240 ZDDP + AO + BPD (3%)

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290

AO/Borates - Friction BPD (1.5%) shows significant reduction in friction starting at around 90°C.

0.16

Coefficient of Friction

0.15

0.14

0.13

0.12

0.11 30°C

50°C

70°C

90°C

110°C

130°C

0.1 Base Grease

1° ZDDP + AO + BPD (1.5%)

1° ZDDP + AO + BPD (1.5%)

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Packages ID

%Zn

%P

%S

%N

Description

4 2 -----

3.5 1.8 1.2 0.8 1.3 1.2

22.9 12.1 36.1 25.6 29.6 32.5

0.1 0.6 0.8 0.9 0.8 1.1

Core ZDDP/Sulfur ZDDP/Sulfur + AO/RI Core S/P Core S/P + AO Core S/P Core S/P

Base Grease ZDDP Pack 1 ZDDP Pack 2 S/P Pack 1

100

S/P Pack 2

S/P Pack 3

S/P Pack 4

97.64

95.54

98.50

97.89

98.18

98.34

Treat rate

2.36

4.46

1.50

2.11

1.82

1.66

S, ppm

5404

5397

5415

5402

5387

5395

P, ppm

826

803

180

169

237

199

Zn, ppm

944

892

0

0

0

0

N, ppm

24

268

120

190

146

183

Treat rates used to deliver equal sulfur levels (~5400 ppm) Confidential and Proprietary - not to be copied, shared,shared, or reproduced in any media the express written permission of AftonofChemical Corporation.

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Packages - TGA

0

-5

ZDDP shows some increase in thermal stability of base grease and AO helps boost stability

-10

-15

-20 50

150

250

Base Grease

350

450 550 Temperature, ⁰C

ZDDP Pack 1

ZDDP Pack 2

650

750

850

ZDDP Pack 2 (2)

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Packages - TGA

0

S/P doesn’t show increased thermal stability in same way; but has some impact on thickener component.

-5

-10

-15

-20 50

150

250

Base Grease

350

450 550 Temperature, ⁰C

S/P Pack 1

S/P Pack 2

650

S/P Pack 3

750

850

S/P Pack 4

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Packages – Rheology 1 0.9 0.8

Dropping Point is 197°C

Tan Delta

0.7

Higher treats of AO in ZDDP Pack 2 show different impact on structural stability

0.6 0.5 0.4 0.3

Presence of ZDDP gives reduction in “liquid” nature at high temp

0.2 0.1 0 40

Temperature, °C Base Grease

90 Base Grease (2)

140 ZDDP Pack 1

190 ZDDP Pack 2

240 ZDDP Pack 2

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Packages – Rheology 1 0.9 0.8

All S/P packages show lack of structural integrity above dropping point

Tan Delta

0.7 0.6 0.5

Dropping Point is 197°C

AO in S/P Pack 2 may cause higher Tan Delta in this region

0.4 0.3 0.2 0.1 0 40

Temperature, °C

90

140

190

Base Grease

Base Grease (2)

S/P Pack 1

S/P Pack 2

S/P Pack 3

S/P Pack 4

240 S/P Pack 1

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Packages – Extreme Pressure/Antiwear Test

ASTM

4 Ball EP, Weld Point, kg 4 Ball Wear (40kg, 75C, 1200 rpm, 1 hr), mm

Base Grease ZDDP Pack 1 ZDDP Pack 2 S/P Pack 1

S/P Pack 2

S/P Pack 3

S/P Pack 4

D 2596

180

240

230

280

270

270

270

D 2266

0.67

0.53

0.45

0.68

0.58

0.52

1.06

290

Weld Load, kg

250

Variability in EP & wear even though same sulfur level

1

0.9

230

0.8

210

0.7

190

0.6

170

0.5

150

0.4 Base Grease ZDDP Pack 1 ZDDP Pack 2 S/P Pack 1 4 Ball Weld

S/P Pack 2

S/P Pack 3

S/P Pack 4

4 Ball Wear

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Wear Scar, mm

270

1.1

Foundational knowledge?

ZDDP Thicker tribolayers can help with protection against wear, corrosion and EP; may also hurt friction and interfere with action of other surface active agents Role as a peroxide decomposer provides secondary oxidation reduction

Sulfur Good protection for EP but at expense of wear; interactions with other componentry can be significant Sulfurized olefin provides antioxidant protection

High temperature AO and boronated dispersant can have positive impact on thermal stability of grease thickener and oil; may offer other benefits as well (corrosion, friction)

Packages Need to balance componentry with performance targets

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Additions Finish study of interactions of main components Rust inhibitor interactions Additional borate/AO data

Compare key critical areas with lithium complex base High temp bearing work to correlate with rheology

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Heavy Lifting Afton Chemical Corp.

Mike Lennon Mike Edwards Mike Jennings Cody Walker Karen Hux Dirk Burmeister

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Questions?

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