A comparative review of the chemistry and

performance of novel synthetic lubricants with

CO2 refrigerant

Liz Dixon Director of Global Technology

Shrieve Group of companies

Shrieve Group of companies, 2012

Common R744 lubricant types

Performance attributes (in R744) influenced by

lubricant type

Preferred lubricant selection for R744 systems

Shrieve Group of companies, 2012

 Di-capped polyalkylene glycol (PAG)

O R1
RO
x

Polyol ester (POE)

O O
x O O x
O O
x x
O O

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 R O
O H O H
O
O

y
x
Single end-capped PAGs

R
O R
O O O R
O

y y

Standard double-end capped PAGs Asymmetric capped PAG

(R usually CH3) (Tetrahydrofuryl starter molecule)

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Compared with symmetrically capped PAGs and uncapped PAGs:

Improved refrigerant solubility profile

Enhanced Extreme Pressure/ Anti-wear properties

Improved thermal stability

Reduced water absorption

Compared with POE:

Preferable refrigerant solubility profile

Hydrolytic stability

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 CO2 solubility:

Where PAG of symmetrical capped or un-capped type:

POE > PVE > PAG > PAO / AB / MINERAL

Where PAG of asymmetrical capped type:

POE > PAG > PVE > PAO / AB / MINERAL

POE demonstrates higher CO2 solubility, but disadvantageous

viscosity reduction may be associated with this

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 Solubility with R744 enhanced compared with uncapped
and symmetrically capped PAGs

Viscosity reduction associated with solubility is minimal

compared with POE

Lubricity property not disadvantaged by improved

solubility

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 Trans-critical CO2 systems - higher load-bearing requirements

Falex Block-on-Ring procedure:

Load steps: 50lb steps, followed by 20lb steps

Rotation: 600 rpm
Atmosphere: CO2
Overpressure: 10 bar (150psi)
Step duration: 5 minutes
Temperature: 90C minimum
Ring / Block: Steel

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Falex Block-on-Ring Summary:

Failure Load
(20 load steps)

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 Symmetric capped Asymmetric Asymmetric
(for R744) Di-capped (for HFC) Di-capped (for R744)

50lb load steps

20lb load steps

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Wear property of capped PAGs by Falex pin & V-block CO2 (1 atmosphere), 100C:

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High Pressure Differential Scanning Calorimetry:
CO2 environment: (1100 Kpa)
Temperature: 0 - 350 C

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 START POINT PEAK END POINT
SAMPLE (C) (C) (C)

VG 46 199.9 215.2 273.8

Asymmetric di-capped
(For R744)

VG 46 193.9 207.3 270.1

Symmetric di-capped

VG 100 191.7 208.1 227.6

Asymmetric di-capped
(For R744)

VG 100 182 201.9 285.1

Symmetric di-capped

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 Water Content (ppm)

Time (mins)

Tendency of PAGs to absorb water is reduced as a result of end-capping

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Hygroscopicity O
PAG water absorption problematic?
POE requires:
Corrosion? Low water specification
for chemical stability.
Freezing within capillaries?
Not required for PAG
Chemical stability?

Water Chemically bound and therefore undesired effects of water not experienced

O O
H H
H H

O O R
R O O

H H
H H
O O

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 Non-reactivity of PAG with water, hygroscopicity non-problematic

PAGs non-reactive with any carbonic acid formed by reaction

of CO2 with water. Carbonic acid further to SGT typically non-detectable

ASHRAE 97 TAN TAN

14days, CO2, 175C, 0.1wt% H2O. (unreacted) reacted
MgKOH/g MgKOH/g

Sample

Asymmetric di-capped: 0.12 0.01

Asymmetric di-capped + 0.1wt% H2O: 0.12 0.01

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 Asymmetric di-capped PAGs fully compatible with alternate PAGs/
POEs, over the full temperature range tested (-20 to +110C). Fully
compatible in all proportions (0-100% components).

Foaming considerations require adequate POE removal (to <2% vol)

when changing-out from POE to PAG.

Stable and compatible with all common synthetic elastomer types.

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Industry example with 85cSt POE for screw compressor:

Potential onset of bearing fatigue after around 2500 hrs. (compared with a
possible design life of 100,000 hrs.)

Problems achieving adequate de-gassing of the POE lubricant which results in

inadequate oil film, reluctance to move to higher viscosity product as same
lubricant required for recips.

Following slide summarises results of a 5000 hour trial with a asymmetric

di-capped PAG

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5000 hr. trial with asymmetric di-capped PAG:
Sample 1 Sample 2 Sample 3 Sample 4 Typical di-capped PAG
Attribute
(unused oil) (47hrs runtime) (1492 hrs runtime) (4781hrs runtime) specification

Clear and bright, free from
Appearance at 20C haze, striation and
particulates
Clear and bright, free from Clear and bright, free from Clear and bright, free from
Clear, slight haze is
haze, striation and haze, striation and haze, striation and
permissable
particulates particulates particulates

Colour (Gdr) <1.0 Gardner <1.0 Gardner <1.0 Gardner 2.0 Gardner 1.0 Gdr maximum

Water content (ppm) 52 53 88 114.3 300-500 maximum

Viscosity at 40C (cSt) 68.45 64.64 66.62 66.11 62.0 74.0

pH 7.10 7.18 6.52 8.01 Non-specification item

TAN (mgKOH/g) <0.01 <0.01 0.16 0.21 Non-specification item

I.R (attach spectrum) No change detected between new and used lubricant.

Oxidation (abs, cm-1) No change detected between new and used lubricant

Nitration (abs, cm ) -1
No change detected between new and used lubricant Non-specification item

Nitrocompounds (abs,
No change detected between new and used lubricant
cm-1)

ICP (ppm) :

Tin <1 <1 <1 18.4

Chromium <1 <1 <1 <1

Iron <1 <1 <1 <1

Lead <1 <1 <1 <1 Non-specification item

Copper <1 <1 <1 <1

Nickel <1 <1 <1 <1

Aluminium <1 <1 <1 <1

Phosphorous <1 <1 <1 68.1

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 Novel capping technology enables the synthesis of PAG type refrigeration
lubricants with application specific properties, e.g. R134a and CO2
compressor applications.

Flexible capping process allows structure modification and hence

performance optimisation for the future refrigerant technology developments.

Primary issue of POE solubility in CO2 - shows evidence of lubricant

compromise, extensive change-outs to di-capped PAG as a consequence.

Asymmetric di-capped PAGs offer a preferable balance of technical attributes

for R744 systems, and are now globally OEM approved.

Please come and see us in Hall 4, Stand 608

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