A State-of-the-Art Colorimetric Patch Analyzer

Akira Sasaki
Maintek Consultant, Yokohama Japan
Kenji Matsumoto
Honda R & D Co., Ltd. Utsunomiya, Japan
Tomomi Honda
University of Fukui, Fukui, Japan

ABSTRACT

In 2013, ASTM announced ASTM D7843 for analyzing oil contamination by color
using commercially available colorimetric spectrometers, which use reflecting light
only. Contaminants in turbine oils are mostly oil oxidation products of molecular sizes.
When warm turbine oil which has been used for several years is filtered through a
membrane filter, the color of the membrane filter may be white. However when the
same oil is filtered after cooled at room temperature in dark for 3-4 days, the color of
the membrane patch sometimes becomes brown. When we examine such an almost-
white membrane patch with back light, we will notice brown color of oil oxidation
products. This paper discusses a newly developed colorimetric patch analyzer to detect
contaminants, which were collected on the surface, by reflecting light and also those,
which were captured inside a membrane filter, by transmitting light.

KEYWORDS

Contamination, turbine oils, oxidation products, molecules, membrane filters

INTRODUCTION

When we see a membrane patch which filters an oil sample, the retina of our eyes
perceive the color of it by reflection light (1). The color of the membrane patch will be
white, when the oil is new or clean but it will be colored when the oil is contaminated.
Therefore examination of the color of the membrane patch will be one of the tools for
oil contamination control. ASTM issued a new standard of ASTM D7843 (2) to measure
insoluble color bodies which are extracted on a membrane patch from in-service turbine
oil using a commercially available colorimetric spectrometer. Commercially available
colorimetric spectrometers measure colors using reflection light, as we see the color of
an object by reflection light. We have experienced that colors of membrane patches,
through which in-service turbines oils are filtered within half an hour after they are
pulled out of oil tanks, are almost white but that they show yellow or brown colors
when the same oils were filtered after cooled at room temperature in dark for 3-4 days.
Such colors can be measured by reflection light. However we have sometimes noticed
that some faintly gray tint exists on almost white membrane patches which filtered
warm oils. When such patches are examined with back light, brown colors can be seen
inside the patches. But they cannot be detected by reflection light. Therefore the authors
have jointly developed a state-of-the-art colorimetric patch analyzer (hereinafter called
as CPA) on the basis of RGB system to examine not only the color of contaminants
collected on the patches using reflection light but also that trapped inside the patches
using transmission light (3). This paper discusses measurement of colors of contaminants
by CAP.

MEASUREMENT OF COLORS OF PATCH SAMPLES

RGB Color System

ASTM D7843 is made on the basis of CIE 1976 L*a*b* color system. But CPA uses RGB
color light system. For RGB color system, R (Red), G (Green), and B (Blue) are the three
primary colors of light. When R is placed on the X axis, G on the Y axis and B on the Z
axis of XYZ coordinate and each color of R, G and B is divided into 256 levels from 0 to
255, R will be expressed by (255, 0, 0), G (0, 255, 0) and B (0, 0, 255). The color of
mixture of R and G light is Y (Yellow) and (255, 255, 0), that of G and B is C (Cyan) and
(0, 255, 255), and that of B and R is M (Magenta) and (255, 0, 255). These Y, C and M
are the three secondary colors of light. When the three primary colors of light are equally
mixed, the color of the light is white (W) and (255, 255, 255). When R is 0, G 0 and B 0,
there is no light and the color is black (K). R, Y, G, K, W, C, B and M make a RGB cubic,
as shown Fig. 1 (4). As any colors of contaminants are almost always on the face of
K,C,W,R or at the side of G of the face of K,C,W,R in the cubic and on the face of
B,W,Y,K or at the side of R of the face of B,W,Y,K in the cubic, they are on or in the
pyramid of W, K R and Y, as shown in Fig. 1 (4).

Fig. 1 RGB Color System in 3-D

Patches of Sample Oils

Five (5) sample oils from gas turbines were kept at room temperature in dark for 3
months for oil oxidation products to be agglomerated in the oils to the extent of stable
conditions. Each 25 ml of them were filtered through a 25 mm membrane filter with 0.8
micron pores made of the mixed materials of nitro-cellulose and cellulose acetate in
accordance with the similar procedure described in the section 9 of ASTM D7843. The
patches, which filtered cooled oils, are shown in the left line of Fig. 1 and are named as
6-L, 7-L, 8-L, 9-L and 10-L. The section 8.2 of ASTM D7843 requires that the sample
shall be heated to 60-65 for 23-25 hours then to be stored at the temperature between
15-25, away from UV light for an incubation period of 68-76 hours. It will be worth
while to demonstrate that the used oil, which has oil oxidation products and has been
kept at room condition for 3 months, can restore, by heating oils to 60-65 for about 24
hours, the same condition that the sample oil was taken from the working oil tank. As
the safety regulation of our laboratory did not allow us to keep on any heater after office
hour, the sample oils were heated at 80 for 8 hours on the assumption that the heating
of oil at 80 for 8 hours is almost equivalent to the heating at 60-65 for 24 hours in
accordance with Arrhenius equation. The patches of Fig. 2 are seen by reflection light.
The patches which filtered the oils heated at 80 for 8 hours are shown in the right
line of Fig. 2 and are named as 6-R, 7-R, 8-R, 9-R and 10-R. The patches of sample oils
which were heated for one and a half hour are shown in the middle line of Fig. 2 and are
named as 6-M, 7-M, 8-M, 9-M and 10-M. As the patches of Fig. 2 are seen by reflection
light, all of the patches are renamed by affixing R letter of reflection light at the tail of
each sample number, as 6-L-R, 7-L-R, 8-L-R, 9-L-R and 10-L-R, as 6-R-R, 7-R-R, 8-R-
R, 9-R-R and 10-R-R, as 6-M-R, 7-M-R, 8-M-R, 9-M-R and 10-M-R respectively.

Fig. 2 The Surface Colors of Membrane Patches Seen with Reflection Light

When the same patches of Fig. 2 were examined by projecting the light from their back
side, brown colors were noticed on all the patches as shown in Fig. 3. It is because
brown colored contaminants existed inside the thin patches, although they were not on
the surfaces of the patches when heated oils were filtered. All of the patches seen by
transmission light are renamed by affixing T letter of reflection light at the tail of each
sample number, as 6-L-T, 7-L-T, 8-L-T, 9-L-T and 10-L-T, as 6-R-T, 7-R-T, 8-R-T, 9-R-
T and 10-R-T, as 6-M-T, 7-M-T, 8-M-T, 9-M-T and 10-M-T respectively.
 Fig. 3 The Photos of the Same Patches Seen with Transmission Light

Measurement of Colors of the Patches Using CPA

The colors of these patches were measured by CPA and the results of the measurement
by reflection light are shown in Table 1.
 Table 1 RGB Readings by Reflection Light and E Values
Patch R G B Maximum differential E
Nos. of R, G, and B values value
6-L-R 230 180 116 114 12.6
6-M-R 233 192 140 93 11.5
6-R-R 235 221 202 33 8.1
7-L-R 227 187 141 86 11.6
7-M-R N/M N/M N/M ---
7-R-R 206 200 194 12 9.8
8-L-R 231 203 160 71 10.5
8-M-R 231 221 206 25 8.1
8-R-R 239 234 217 22 6.8
9-L-R 210 155 62 148 14.9
9-M-R 236 218 189 47 8.8
9-R-R 240 236 218 22 6
10-L-R 221 162 95 126 13.7
10-M-R 227 186 128 99 12.1
10-R-R 230 203 167 63 10.3

The results of the measurement by transmission light is shown in Table 2.

Table 2 RGB Readings by Transmission Light and E Values

Patch R G B Maximum differential E
Nos. of R, G, and B values
6-L-T 172 113 37 135 16.5
6-M-T 172 127 48 124 16
6-R-T 184 135 66 118 15.5
7-L-T 169 106 41 128 16.6
7-M-T N/M N/M N/M ---
7-R-T 89 66 25 64 17.6
8-L-T 187 122 36 151 16.3
8-M-T 214 162 37 177 15.5
8-R-T 225 180 46 179 15
9-L-T 175 132 59 116 15.6
9-M-T 210 161 67 143 14.7
 9-R-T 220 180 78 142 14.0
10-L-T 154 88 17 137 17.5
10-M-T 167 102 23 144 17.1
10-R-T 181 122 48 133 16

The color of each patch is shown by R, G, and B values and the distance (E) between
the color point (R, G, B) and the white point (255, 255, 255) can be calculated by the
following equation.

E = (255R)2 + (255G)2 + (255B)2 (1)

TheE value shows how far the color point is deviated from the white point which is the
original color of a new patch. When each R, G and B value is 0 in an extreme case, the
value ofE is 442 and when each of them is 255, the value ofE is 0. As the difference
ofE values is very large, it is convenient to use the square root of E to condense the
readings of 442 to 21. The Table 1 and Table 2 show the E values. In order to
interpret the E values, two Tables are shown in Appendix I (Interpretation of
E value by reflection light) and II (Interpretation of E value by transmission light).
The maximum differentials of the three values of R, G and B (it is the differential between
the value of R and that of B or G) are calculated and shown in Tables 1 and 2.

Measurement of Patch Colors Using A State-of-the-Art Colorimetric Patch

Analyzer

The colors of the patches filtered cooled oils and heated oils of sample Nos. 6-10 which
are measured by reflection light and by transmission light are shown in the graphs of
Fig. 4-8. The maximum differentials of R, G and B values of the patches measured by
transmission light of cooled oils are large and those of heated oils are also large. It is
because CPA measures the colors of oil oxidation products on the surfaces of the
patches by reflection light and measures those inside the patches, which filtered heated
oils, by transmission light.
 The Difference of Patch Colors
between Cooled Oil and Heated Oil
of Sample No. 6
250
200
150
100
50
0
6-L-R 6-R-R 6-L-T 6-R-T

R G B

Fig. 4 A Graph of Change of Colors of the Patches Which Filtered Cooled Oil and
Heated Oil of Sample No. 6 by Reflection Light and by Transmission Light
(Left: by Reflection Light R at the tail and
Right: by Transmission Light T at the tail)

The Difference of Patch Colors

between Cooled Oil and Heated Oil
of Sample No. 7
250
200
150
100
50
0
7-L-R 7-R-R 7-L-T 7-R-T

R G B

Fig. 5 A Graph of Change of Colors of the Patches Which Filtered Cooled Oil and
Heated Oil of Sample No. 7 by Reflection Light and by Transmission Light
(R at the tail: by Reflection Light, and T at the tail: by Transmission Light)
 The Difference of Patch Colors
between Cooled Oil and Heated Oil
of Sample No. 8
300
250
200
150
100
50
0
8-L-R 8-R-R 8-L-T 8-R-T

R G B

Fig. 6 A Graph of Change of Colors of the Patches Which Filtered Cooled Oil and
Heated Oil of Sample No. 8 by Reflection Light and by Transmission Light
(R at the tail: by Reflection Light, and T at the tail: by Transmission Light)

The Difference of Patch Colors

between Cooled Oil and Heated Oil
of Sample No. 9
300
250
200
150
100
50
0
9-L-R 9-R-R 9-L-T 9-R-T
R G B

Fig. 7 A Graph of Change of Colors of the Patches Which Filtered Cooled Oil and
Heated Oil of Sample No. 9 by Reflection Light and by Transmission Light
(R at the tail: by Reflection Light, and T at the tail: by Transmission Light)
 The Difference of Patch Colors
between Cooled Oil and Heated Oil
of Sample No. 10
250
200
150
100
50
0
10-L-R 10-R-R 10-L-T 10-R-T

R G B

Fig. 8 A Graph of Change of Colors of the Patches Which Filtered Cooled Oil and
Heated Oil of Sample No. 10 by Reflection Light and by Transmission Light
(R at the tail: by Reflection Light, and T at the tail: by Transmission Light)

DISCUSSION

The photos of Fig. 2 show the colors of the surfaces of the patches. The colors can be
perceived by the light which reflected on the contaminants on the patch surfaces. The
patches of 6-L-R, 7-L-R, 8-L-R, 9-L-R and 10-L-R in Fig. 2 which filtered cooled oils
have brown or light brown colors. It suggests that all oils have brown-colored
contaminants, which are agglomerated to larger particles than the pore of the patches.
However the patches of 6-R-R, 7-R-R, 8-R-R, 9-R-R and 10-R-R in Fig. 2 which
filtered heated oils are almost colorless. It suggests that almost all contaminants in oils
might have disappeared by heating. However the photos of all the patches of Fig. 3,
which were taken with backlight, show brownish colors. They show the colors by the
light which are transmitted through the patches from the other side of the patches. The
patches which filtered heated oil, do not show by reflection light but the same patches
examined by transmission light show that contaminants existed in the patches. It
suggests that the contaminants are smaller than the pore sizes of the patches and that
such small particles are captured inside the patches.
From the stand point of preventive and proactive maintenance, it is not good to overlook
existence of contaminants in oils. A state-of-the-art colorimetric patch analyzer has been
developed to measure colors of contaminants on the surface of a membrane patch by
reflection light and those captured inside the membrane patch by transmission light.
Measurement by Reflection Light

The left graphs of Fig. 4 to Fig. 8 show the R, G and B of the patches filtered the cooled
oils and the heated oils measured by reflection light. The R, G and B values of the
cooled oils diverge but those of the heated oils converge. Therefore the maximum
differential values (MDV) of R, G and B by reflection light of the patches which filtered
cooled oils are larger than those of the patches filtered heated oils as shown in Table 3
and Table 4.

Table 3 The Max. Differential Values of R, G, B by Reflection Light

of the Patches of Cooled Oils and E Values
Patch Nos. 6-L-R 7-L-R 8-L-R 9-L-R 10-L-R
MDV (MDV) 114 (10.7) 86 (9.3) 71 (8.4) 148 (12.2) 125 (11.2)
E Values 12.6 11.6 10.5 14.9 13.7

Table 4 The Max. Differential Values of R, G, B by Reflection Light

of the Patches of Heated Oils
Patch Nos. 6-R-R 7-R-R 8-R-R 9-R-R 10-R-R
MDV(MDV) 33 (5.7) 12 (3.5) 23 (4.8) 22 (4.7) 63 (7.9)
E Values 8.1 9.8 6.8 6 10.3

The small MDV shows that the color is near the black (K)-white (W) diagonal line of
Fig. 1 and the large MDV shows that the color deviates from the K-W diagonal line to
the side of red and yellow colors (4). The paper of reference No. 4 analyzed mainly on
hydraulic oils. The majority of hydraulic oils, which were examined at that time, used
zinc based additives which produced relatively a lot of decomposed zinc compounds.
Therefore the paper proposed to classify the maximum differential values in the group
of A to K. The groups of A to J had ten (10) gaps like 1 to 10 and 11 to 20 at each group
and K group had the maximum gap from 101 and over (4). However the colors of
contaminants of turbine oils are brown and/or light brown and the maximum differential
values are larger than 50 in general, as they do not use zinc based additives and do not
produce a lot of decomposed zinc base compounds.
Therefore the authors propose new classification tables for the maximum differential
values somewhere else. As the single metal like Fe, Ni, Co, Mn, which compose of
many metal alloy, have silver white color, the colors of the patches are near on the line
between white and black, when oils having these metal particles are filtered through
membrane patches. The Fig. 2 and Tables 3 and 4 show that the colors of the patches of
cooled oils are brown and their MDV are large but that the colors of the patches of
heated oils are light and their MDV are small. However the patch of the heated oil (7-R-
R) shows light gray color which indicates that metallic particles or particles from the
environment are predominant over oil oxidation products on the patch surface. It
corresponds to the small MDV. Therefore this kind of phenomena will be overlooked if
we do not check the colors of the patches of heated oils by sticking to the procedure of
ASTM D7843.

Measurement by Transmission Light

The Fig. 3 photo shows that not only the colors of the patches of cooled oils but also
those of heated oils are brown, because brown-colored oil oxidation products are
captured inside the thin patches. The colors of the patches measured by transmission
light (T of the tail of patch number means transmission light) are different from
those measured by reflection light. The maximum differential values (MDV) of R, G
and B by transmission light of the patches which filtered cooled oils are shown in Table
5 and those of heated oils in Table 6.

Table 5 The Max. Differential Values of R, G, B by Transmission Light

of the Patches of Cooled Oils and E Values
Patch Nos. 6-L-T 7-L-T 8-L-T 9-L-T 10-L-T
MDV(MDV) 135 (11.6) 128 (11.3) 151 (12.3) 116 (10.8) 137 (11.7)
E Values 16.5 16.6 16.3 15.6 17.5

Table 6 The Max. Differential Values of R, G, B by Transmission Light

of the Patches of Heated Oils
Patch Nos. 6-R-T 7-R-T 8-R-T 9-R-T 10-R-T
MDV(MDV) 118 (10.9) 64 (8) 179 (13.4) 142 (11.9) 133 (11.5)
E Values 15.6 17.6 15 14 16

The graphs of Figs. 4 to 8 show that each R, G, and B value of the other patches of
heated oils becomes large and their MDV maintains large except the patch No. 7-R-T. It
suggests that the oil oxidation products to be captured on the surface of the patches are
large in volume when cooled oils are filtered, but that they are small when heated oils
are filtered. This is correlated to the fact that the value of the maximum differential of
each R, G, and B of the 7-R-R patch was very small by reflection light and the visual
color of the patch looks gray, when the heated oil was filtered. It is because wear
metals and/or the contaminants from the environment, which are insoluble in oil,
became dominants, as the oil oxidation products became soluble in oil by heating the
oil. The fact also suggests that measurement of the color of the patch which filtered
heated oil is important to know the contaminants in oil.

Behaviors of Oil Oxidation Products

Then it is important for us to understand the meaning of soluble of oil oxidation

products. It is known that the molecular weight of oil oxidation products are in the
range of 500 to 100,000 (5) and that oil oxidation products with the molecular weight in
the range of 550 to 1900 are soluble in oil at about 60-65 but become insoluble in oil
when oils are cooled to room temperature for a few days (6). In the cases of gas turbine,
oil flow velocity of bearing cooling system is very fast in the range of 2000 L/min to
3900 L/min. When oil passes through filter media, static electricity will be generated.
The static electricity will be accumulated on the dielectric materials like filter fibers and
oil. It will be discharged with sparks at any sharp points which are connected to the
ground. Spark discharges of it will crack oil molecules and lead to oil oxidation (7)-(9).
Therefore the majority of contaminants in used oils especially in turbine oils are oil
oxidation products (5). The molecules of hydrocarbon base oil are non-polar but oil
oxidation products having oxygen molecules therein form dipole and have polarity, as
oxygen molecules have larger electronegativity than hydrogen. As oil oxidation
progresses, the molecules of oil oxidation products become lager in the form of trimer,
tetramer, and finally to polymers of high molecular weight oxidation products (10). Polar
molecules are incompatible with non-polar ones. As polar molecules are minority in
non-polar oil, they form dimer by making polar groups face each other and directing
hydrocarbon parts to oil as shown in Fig. 9 (a) (5). In such a manner, they also form
micelles as shown in Fig. 9 (b) (11). Then they can friendly coexists with oil molecules.
They are still nanoparticles in oil and behave as if they are soluble in oil, as their motion
is large when oil temperature is high.

Fig. 9 Polar molecules form (a) a dimer and (b) a micelle

When the oil having such nanoparticles is filtered through a membrane patch, they are
too small to be captured on the surface of the membrane patch. However the fibers of
the membrane patch will be electrified when oil passes through them. Therefore
nanoparticles will be drawn by the Coulomb force of static electricity and trapped on the
fibers of the oil passages of the membrane patch, although they are not captured on the
surface. When oil is cooled, the motion of nanoparticles will become slow. Then they
will be agglomerated to form large particles to reduce the total surface area of particles.
Such particles will take the shapes of balls because of the surface tension. When the
number of them increases and they can grow larger in size than the pores of the patch,
they will be captured by the surface pore of the patch to form a cake. It is the reason
why a membrane patch shows colors when cooled oil is filtered through a membrane
patch.

SUMAMRY AND CONCLUSION

1 Turbine oils were filtered when oils are cooled and heated and the colors of
membrane patches were measured using a state-of-the-art colorimetric patch
analyzer which uses both reflection light and transmission light on the basis of RGB
color system.
2 The colors of the patches which filtered cooled oils showed brown colors and light
brown colors but those filtered heated oils did not show brown colors, when they
were measured by reflection light, as the colored contaminants were oil oxidation
products which were insoluble in oil when the oils were cooled but became soluble
in oil when the oils were heated.
3 The colors of the same patches showed brown color, when they were measured by
transmission light. It suggests that oil oxidation products in heated oils were in the
state of nanoparticles and they were drawn and caught inside the patches by static
electricity. This phenomena cannot be detected by reflection light but can by
transmission light.

REFERENCE
(1) Young, T., On the Theory of Light and Colours, Phil. Trans. Vol. 92 (1802),
pp.12-48.
(2) ASTM, D7843, Standard Test Methiods for Measurement of Lubricant
 Generated Insoluble Color Bodies in In-Service Turbine Oils using Membrane
Patch Colorimetry.
(3) US patent No. 8390796 B2, Mar. 5 2013.
(4) Yamaguchi, T., Kawamura, S., Honda, T., Ueda, M., Iwai, Y. and Sasaki, A.,
Investigation of Oil Contamination by Colorimetric Analysis, Lubr. Engr. 58, 1
(2001), pp. 12-17.
(5) Sasaki, A., Contaminants in used oils and their problems, Proc. IMechE.Vol.
220, Part J., J. Eng. Tribo. (2006), Special Issue Paper 471.
(6) Sasaki, A., Aoyama, H., Honda, T., Iwai, Y. and Yong, C.K., A Study of the
Colors of Contamination in Used Oils, Tribo. Trans. 57, (2014), pp. 1-10.
(7) Sasaki, A., Varnish Formation in the Gas Turbine Oil Systems, J. ASTM Intl,
Vol. 5 No. 2, Pape ID JS101419.
(8) Sasaki, A., Uchiyama, S. and Yamamoto, T., Generation of Static Electricity
During Oil Filtration, Lubr. Engr. 55, 9 (1999) pp. 14-21.
(9) Sasaki, A., Uchiyama, S. and Yamamoto, T., Free Radical and Oil Auto-
Oxidation Due to Spark Discharges of Static Electricity, Lubr. Engr. 55, 9 (1999)
pp. 24-27.
(10) Cho, L., and Klaus, E.E., Oxidative Degradatio of Phosphate Esters, ASLE
Trans. 24 (1981) pp. 119-124.
(11) Maeno, M., Characteristics of nano-particles (Science of colloids and interface)
(in Japanese), Blue backs, B1392 (Monograph), Kodansha Co., Ltd. Tokyo, Japan.
APPENDIX I
Classification of ERGB Values by Reflecting Light
Class 1 2 3 4 5
ERGB Smaller 9.1 - 12 12.1 - 15 15.1 - 17 Larger than
Value than 9 17.1
Judgment Good Safe Watch Caution Critical
Comments Well Oxidation Polymerized Polymerized Take
maintained products oxidation oxidation immediate
start to products products actions for
form start to form increase. preventing
Prepare for oil machine
cleaning or oil problems
change

APPENDIX II
Classification of ERGB Values by Transmitting Light
Class 1 2 3 4 5
ERGB Smaller 15.1 - 17 17.1 - 19 19.1 - 20 Larger than
Value than 15 20.1
Judgment Good Safe Watch Caution Critical
Comments Well Oxidation Polymerized Polymerized Take
maintained products oxidation oxidation immediate
start to products products actions for
form start to form increase. preventing
Prepare for machine
oil cleaning problems
or oil
change