U.S. patent application number 10/529969 was filed with the patent office on 2005-11-03 for system for identifying the lubricating oil in a machine.
This patent application is currently assigned to Shell Oil Company. Invention is credited to Sant, Peter, Taylor, Robert Ian.
Application Number | 20050241989 10/529969 |
Document ID | / |
Family ID | 9945081 |
Filed Date | 2005-11-03 |
United States Patent
Application |
20050241989 |
Kind Code |
A1 |
Sant, Peter ; et
al. |
November 3, 2005 |
System for identifying the lubricating oil in a machine
Abstract
A lubricating oil identification system including a lubricating
oil composition containing a passive marker which passive marker is
capable of detection in situ by a detector present in a machine is
provided. A detector is provided for detecting in situ a passive
marker in the oil composition when the oil composition is in the
machine. Lubricating oil compositions and machines suitable for use
in this identification system and methods of operating the machines
are also disclosed.
Inventors: |
Sant, Peter; (Chester,
Cheshire, GB) ; Taylor, Robert Ian; (Chester
Cheshire, GB) |
Correspondence
Address: |
SHELL OIL COMPANY
P O BOX 2463
HOUSTON
TX
772522463
|
Assignee: |
Shell Oil Company
P.O. Box 2463 910 Louisiana
Houston
TX
77252-2463
|
Family ID: |
9945081 |
Appl. No.: |
10/529969 |
Filed: |
June 29, 2005 |
PCT Filed: |
October 1, 2003 |
PCT NO: |
PCT/EP03/50674 |
Current U.S.
Class: |
208/18 ;
436/56 |
Current CPC
Class: |
Y10T 436/13 20150115;
C10N 2030/34 20200501; C10N 2040/42 20200501; C10M 171/00 20130101;
G01N 33/2882 20130101 |
Class at
Publication: |
208/018 ;
436/056 |
International
Class: |
C10G 071/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 1, 2002 |
GB |
0222728.8 |
Claims
1. A lubricating oil composition comprising one or more passive
markers capable of detection in situ by a detector present in a
machine which is on or running.
2. The lubricating oil composition of claim 1 wherein the passive
markers are microparticles.
3. The lubricating oil composition of claim 1, wherein the passive
markers are molecular species.
4. The lubricating oil composition of claim 2 wherein the passive
markers are selected from the group consisting of Radio Frequency
Identification chips, biomagnetic tags and magnetic tags.
5. A method of making a lubricating oil composition comprising
providing a lubricating oil and incorporating one or more passive
markers into said lubricating oil which passive markers are
suitable for detection in situ by a detector present in a machine
which is one or running.
6. The method of claim 5 wherein the passive markers are selected
from the group consisting of Radio Frequency Identification chips,
magnetic tags, biomagnetic tags and odourant molecules.
7. A machine comprising a detector capable of detecting a passive
marker in the lubricating oil composition while the machine is on
or running when the lubricating oil composition contains one or
more passive markers capable of detection in situ by said
detector.
8. The machine of claim 7 wherein the machine further comprises an
electronic control unit.
9. The machine of claim 7 wherein the machine further comprises at
least one sensor that indicates the state of the lubricating oil in
the machine.
10. The machine of claim 7 wherein the detector is selected from
the group consisting of .mu.-readers, magnetic readers, electronic
noses, and electronic tongues.
11. The machine of claim 7 wherein the machine further comprises a
pH sensor that is capable of providing a reading that can be
correlated to the Total Acid Number of the lubricating oil.
12. The lubricating oil composition of claim 3 wherein the passive
markers are odorant molecules.
13. The lubricating oil composition of claim 1 wherein the passive
markers are of a size such that they will pass through an oil
filter in the machine.
14. The lubricating oil composition of claim 1 wherein the passive
markers are of a size such that they will not pass through an oil
filter in the machine.
15. A method of operating a machine comprising (a) providing a
lubricating oil into the machine comprising (i) a detector and (ii)
an electronic control unit or machine management chip, (b)
detecting whether or not a passive marker is present in said
lubricating oil thereby providing data about the lubricating oil,
and (c) passing a signal from the detector to the electronic
control unit or machine management chip.
16. The method of claim 15 wherein the signal is processed at the
electronic control unit or machine management chip.
17. The method of claim 15 wherein the data is processed to
determine when an oil change is required or to set values which can
be used to determine when an oil change is required.
18. The method of claim 15 wherein the machine further comprises a
pH sensor.
19. The method of claim 18 wherein further reading the pH of the
lubricating oil thereby providing data about the state of the
oil.
20. The method of claim 18 wherein the data are processed thereby
providing information about the state of the oil to a user or a
machine management system.
Description
[0001] The present invention relates to a system for identifying a
lubricating oil in situ in a machine such as an engine. In
particular, the present invention relates to a lubricating oil
containing passive markers capable of detection in situ in a
machine such as an engine.
[0002] Currently the fluids in an engine, for example, the
lubricant and fuel, represent one of the very few aspects of an
engine about which an engine management chip receives limited, if
any, information on. If the wrong lubricant is used in an engine,
sub-optimum vehicle performance and even engine failure can result.
Therefore, in order to ensure satisfactory and reliable engine
operation, the producer of a vehicle (the Original Equipment
Manufacturer, OEM) usually recommends the use of specific
lubricants. It would be useful if the engine management system was
able to identify the lubricant being used in situ so that it can
inform the user or adjust engine operation accordingly in order to
prevent or diagnose engine problems.
[0003] Different types of lubricating oil require different time
periods between oil changes. It may be that there is more than one
recommended lubricant for an engine, e.g. one product may be of a
standard quality having a given time period between oil changes and
a second product may be of higher quality and be capable of
remaining in the engine for a longer period of time before an oil
change is necessary. It would be useful if the engine management
system could distinguish between different types of lubricant and
be able to use this information to determine when an oil change is
necessary and to indicate this to the vehicle user accordingly.
[0004] Previous attempts to develop means for identifying
lubricating oils have mainly involved incorporating dyes into the
oil, for example as described in U.S. Pat. No. 5,928,954 and
EP-A-1001003.
[0005] For example, U.S. Pat. No. 5,928,954 describes a method for
tagging hydrocarbons such as gasoline, diesel fuel, heating oil,
lubricating oil or crude petroleum, wherein the hydrocarbon to be
tagged is blended with a relatively small amount of a fluorescent
dye. The presence of the tagged hydrocarbon is subsequently
determined by exciting the dye to fluoresce at wavelengths in the
higher portion of the visible spectral region or the lower portion
of the near infrared spectral region.
[0006] Similarly, U.S. Pat. No. 5,525,516 discloses a method for
imparting invisible marking for identification purposes to
petroleum hydrocarbons by incorporating one or more near infrared
fluorescing compounds (fluorophores) therein. The fluorophores are
detected by exposing the marked hydrocarbon compositions to near
infrared radiation having a wavelength in the 670-850 nm range and
then detecting the emitted fluorescent light via near infrared
light detection means.
[0007] EP-A-0637743 describes a method for allowing authentication
of a bulk liquid and a method for detecting subsequent dilution of
a bulk liquid. Said methods are said to involve introducing a known
amount of a chemiluminescent marker substance into undiluted bulk
liquid. The bulk liquid to be authenticated or analysed for
subsequent dilution is then sampled and said samples are exposed to
the conditions required to trigger a chemiluminescent reaction. If
a reaction occurs, authenticity is thereby confirmed. Comparison of
the characteristics of any reaction with those characteristics
corresponding to an undiluted bulk liquid allow determination of
whether or not dilution of the bulk liquid has occurred.
[0008] U.S. Pat. No. 5,942,444 describes a method of marking a
product for identification in which a marker, composed of a print
molecule, print molecule analogue, or molecularly imprinted
molecule, is added to the product and is subsequently measured in a
specific binding assay. It is indicated in U.S. Pat. No. 5,942,444
that producing a sample of a product to assay for a marker will
comprise one or more steps selected from extraction of a marker
compound from the product; dilution of the product with an aqueous
or an organic solvent; filtration; evaporation; precipitation; and
solid phase extraction of the marker compound, e.g. purification of
the marker compound using an ion exchange resin, chromatography
(e.g. using silica), or molecularly imprinted solid phase
extraction (MISPE) chromatography.
[0009] U.S. Pat. No. 5,429,952 discloses a method of marking a
product and subsequently detecting the marker in the product as a
means of identifying the product, comprising the steps of
associating a hapten as a marker with the product, wherein the
hapten is non-deleterious to the product, inert with respect to the
product, and not already associated with the product; and detecting
the hapten in the product at a later point in time as a means of
identifying the product by specifically binding the hapten to a
complementary binding member. Whilst it is indicated that oil-based
products such as lubricating oils, gasoline, diesel and liquefied
petroleum products may be marked and analysed by the method of U.S.
Pat. No. 5,429,952, immunoassay requires the marker to be brought
into aqueous solution. In the case of a marked oil-based product,
this is said to require solvent extraction. Indeed, in this regard,
Example 3 of U.S. Pat. No. 5,429,952 illustrates the assay of a
marked lubricating oil comprising extraction of the
m-phenoxybenzoic acid marker therein with 5 volumes of hexane and 1
volume of 20% acetonitrile in 0.05 M Tris/HCl pH 7.5 prior to
immunoassay.
[0010] U.S. Pat. No. 5,776,713, which is a continuation-in-part of
U.S. Pat. No. 5,429,952, describes a similar method to that
described in U.S. Pat. No. 5,429,952, wherein the marker is a
hapten which is covalently bound to a pre-formed polymeric
compound.
[0011] WO-A-96/00271 describes the use of carbonyl compounds for
marking hydrocarbons such as motor fuels, heating oils and engine
oils. However, detection of said compounds requires treatment of a
sample of said hydrocarbons with a solution of an iron (III) salt
in aqueous alcohol or aqueous acetone. For example, it is indicated
that testing of hydrocarbons which are in a liquid state of
aggregation at standard temperature and pressure is usually carried
out by vigorously shaking about 20 ml of the marker-containing
hydrocarbon with about 2 ml of reagent solution for about 15 to 20
seconds. Upon phase separation, the lower aqueous phase will have
undergone a colour change.
[0012] The problem with the above prior methods is that in order to
identify a lubricant in an engine, a sample of the lubricant has to
be removed from the engine for analysis. As a result these methods
are generally inconvenient and time-consuming and, in particular,
they are not suitable for providing data to an engine management
chip.
[0013] Methods of identifying lubricants whilst in the engine have
been developed but identification is based on relatively crude
information such as the viscosity of the oil. In U.S. Pat. No.
5,274,335, an on-board sensor comprising two spaced apart
electrodes, a triangular waveform means, a comparison means and a
signal means gives an indication of the metallic content of the oil
in order to distinguish between two- and four-stroke oils. The
information that can be provided about the oil in prior art
on-board measurements is limited and, e.g., cannot be used to
distinguish between different brands of lubricating oil.
[0014] There remains a need for an improved system for identifying
lubricating oils in engines that avoids the problems presented by
the above prior methods.
[0015] The present invention provides a lubricating oil composition
which comprises one or more passive markers which passive markers
are capable of detection in situ by a detector present in a machine
such as an engine.
[0016] The passive marker provides information about the identity
of lubricant, e.g. a specific lubricating oil (i.e. one
characterised by brand name and/or performance specification and/or
viscosity grade, etc.) will have a unique marker added to it. It
has been found that by purposively adding identifying markers to a
lubricating oil, which markers are capable of detection in situ in
a machine such as an engine, not only can more accurate and
specific information be provided as to the identity of the oil but
this information can be advantageously utilised by the machine's
electronic control unit or management chip. The lubricating oil of
the present invention, when used in a suitable machine (e.g. an
engine), enables the machine management chip to distinguish between
brands or grades of lubricating oils and react accordingly e.g., by
informing the user and/or adjusting machine operation accordingly.
This lubricating oil may also be used to ensure that fraudulent
lubricating oils are not used in machines such as engines.
[0017] Preferably the passive markers are capable of being detected
in situ in machine which is on or running.
[0018] By "machine" is meant any mechanical equipment having a
lubricating system and includes industrial machines and engines,
for example automotive engines.
[0019] The markers are "passive" in that, in operation, they do not
substantially interfere with the performance of the lubricating
oil, they do not contribute to the lubricating function of the oil
and they do not form a standard component of the oil.
[0020] Passive markers suitable for the identification system of
the present invention include microparticles and molecular species.
Examples of suitable microparticles are Radio Frequency
Identification (RFID) chips, magnetic tags and biomagnetic tags.
Examples of suitable molecular species are odourant molecules.
[0021] In one aspect of the invention, the markers are of a size
such that they will pass through an oil filter in the machine (e.g.
an engine) in which the oil is intended for use. In this aspect of
the invention, preferably the marker is a molecular species, e.g.,
an odourant molecule capable of detection by an electronic nose.
Preferably the marker is an odourant molecule. The choice of
odourant molecule is not limited in the present invention. However,
preferably it is chosen from "Ralley", "Blue Spirit", "Lemon Top"
or "Petrolica" (all manufactured by Symrise (previously known as
Dragoco)). Where the marker is an odourant molecule preferably it
is present in the lubricating oil composition in an amount of 0.01
to 0.5% by volume. Microparticles such as RFID chips, magnetic tags
or biomagnetic tags of a small enough size are also suitable for
this aspect of the invention.
[0022] In another aspect of the invention, the passive markers are
of a size such that they will not pass through an oil filter in the
machine (e.g. an engine) in which the oil is intended for use. In
this aspect of the invention, preferably the markers are
dimensioned so that they will not pass through filter mesh sizes of
between 5 to 50 microns. The concentration of markers in the
lubricating oil is such that they will not substantially interfere
with the operation of the oil filter. Preferably the lubricating
oil comprises from 1 to 10 passive markers per 4 litres of
lubricating oil. In this aspect of the invention, preferably the
markers are Radio Frequency Identification (RFID) chips or magnetic
tags. More preferably the marker is an RFID chip.
[0023] An example of a suitable RFID chip is the Hitachi .mu.-chip
(see Example 1 for details). In operation, the markers are
collected in the oil filter where they are detected by the
detector. The captured markers can then be removed from the oil
filter at the next oil change. They may then be recycled or
discarded.
[0024] In another aspect of the present invention there is provided
a method for providing a lubricating oil suitable for use in the
above-described identification system comprising providing a
lubricating oil and incorporating one or more passive markers into
said lubricating oil which passive markers are suitable for
detection in situ by a detector present in a machine. Incorporation
of the one or more passive markers into the lubricating oil may be
done, for example, at the lubricant blending plant.
[0025] In another aspect of the present invention there is provided
the use of one or more of a Radio Frequency Identification (RFID)
chip, a magnetic tag, a biomagnetic tag and an odourant molecule as
a passive marker for a lubricating oil.
[0026] In another aspect of the present invention there is provided
a machine such as an engine comprising a detector for detecting in
situ a passive marker in the above-described lubricating oil
compositions.
[0027] The choice of detector will depend on the choice of passive
marker, and to a certain extent the position of the detector in the
machine will also depend on the choice of passive marker.
[0028] An RFID .mu.-chip may be detected by a .mu.-reader (see
Example 1 for details) and if the RFID chip is of a size such that
it is captured by the oil filter, then the .mu.-reader may be
positioned on or near the oil filter.
[0029] A magnetic tag which takes a form similar to a bar code,
where the bars in the code are made, from a very soft (low
coercivity), high permeability, magnetic alloy, may be read or
detected using a magnetic reader. A suitable magnetic reader is,
for example, the magnetic reader of U.S. Pat. No. 6,371,379 adapted
for use in an engine or machine. The reader creates a narrow region
of zero field (a null) in space, surrounded by regions where the
field strength is sufficient to saturate the magnetic material used
in the tag. Typically a low amplitude alternating magnetic field is
applied to the interrogation region so that a soft magnetic element
in the null region is driven into and out of saturation, thereby
radiating harmonics of the interrogation frequency. These harmonics
can be detected and their time of occurrence related to the
position of the element with respect to the null. Typically a
spatial resolution of greater than 50 microns can be achieved for a
reader-to-tag separation of many millimetres as described in U.S.
Pat. No. 6,371,379.
[0030] A suitable detector for an odourant molecule is an
electronic "nose", e.g. a surface acoustic wave electronic nose, or
an electronic "tongue". Another suitable electronic nose is one
based on a sensor array which detects vapours. For example, the
sensor array utilised in the device commercially available under
the trade designation "Cyranose 320 Electronic Nose" ex. CYRANO
Sciences Incorporated adapted for use inside an engine or machine
would be suitable (see Example 2). For a given lubricant a sensor
array gives a unique smell print. The sensor array will be able to
detect whether or not the lubricating oil contains a unique
odourant and furthermore will also be able to detect whether or not
the oil is fresh or partially oxidised.
[0031] Preferably the machine (e.g. an engine) comprises an
electronic control unit and signals can be transmitted from the
detector to said electronic control unit. This may be done either
electrically by a wire or by radio frequency techniques at an
appropriate frequency including that of 2.45 GHz corresponding to
Bluetooth technology. Preferably the machine comprises means to
transmit a signal from the detector to the electronic control
unit.
[0032] In operation, a lubricating oil is put into a machine (e.g.
an engine) containing a detector. The detector in the machine will
detect whether or not a passive marker is present. The detector
accordingly passes a signal to the machine management chip in the
machine's electronic control unit. The machine management chip will
either recognise the lubricating oil as an oil approved for the
machine or as an oil not approved for the machine. In the latter
case, this may be as a result of no marker being present. The
machine management chip will process this information accordingly.
For example, if the lubricant is not approved for use in that
machine, then a warning signal may be given to the, e.g., vehicle
user and the machine management chip could flag the use of
non-approved lubricant to the servicing garage the next time the
vehicle has a maintenance check. If the lubricant is approved for
use, the machine management chip will adjust the time period until
the next oil change in accordance with that particular oil's
specification. The machine management chip may process the received
information by adjusting the oil change interval prediction
algorithm.
[0033] Accordingly the present invention provides a method of
operating such a machine comprising:
[0034] (i) using the detector to provide data about the identity of
the lubricating oil in the machine; and
[0035] (ii) utilising the data obtained in (i) to determine when an
oil change is required or to set values which can be used to
determine when an oil change is required.
[0036] In another aspect of the present invention the machine
further comprises at least one sensor which indicates the state of
the lubricating oil in the machine.
[0037] Preferably the sensor measures a parameter which varies with
the rate of degradation of the oil in the lubricant system, for
example the sensor may provide a measurement as to how oxidised the
oil is. The sensor may measure one or more of the following
properties of the oil: viscosity, oil level, temperature, pressure,
alkalinity/acidity, dielectric constant, capacitance, conductivity
and specific density.
[0038] In a preferred embodiment, the machine further comprises a
pH sensor which gives a reading that is correlated to the Total
Acid Number (TAN) of the oil. When the antioxidant of the lubricant
is depleted the TAN will start to rise rapidly, indicating that the
oil should be changed. In this aspect of the invention, information
about the state of the oil may then be used, along with information
about the identity of the oil, by the user or the machine
management system, to determine when the next oil change is due.
This method provides a more accurate determination of when the next
oil change is due than those of the prior art. This is because not
only does it take into account the specification of the particular
oil, it also takes into account the actual state of the oil.
[0039] For example, with regard to engines, the period between oil
changes as recommended by the OEM is frequently based on time
and/or distance travelled (e.g. frequently a handbook may say that
the oil needs changing every year or 9000 miles whichever occurs
first). However, this does not take into account the effect
different types of engine use have on the lubricant. High speed,
long motorway journeys typically put less "stress" on the oil than
frequent cold starts and short trip journeys. By utilising a
measurement of the state of the oil to assess when an oil change is
necessary, the effect that driving conditions has had on the oil is
inherently taken into account.
[0040] Where the passive marker is an odourant molecule, the
detector may also advantageously act as a sensor which indicates
the state of the lubricating oil in the engine or machine. The
smell of oil changes as oil ages and this change may be used as an
indication of the state of the oil and therefore as an indication
of when the next oil change is due.
[0041] Preferably the machine comprises means to transmit a signal
from at the least one sensor to the machine's electronic control
unit or the machine management chip.
[0042] In operation, if the machine further comprises a sensor for
measuring the state of the oil, this sensor will also pass a signal
to the machine management chip. The machine management chip will
process the information accordingly, e.g. by using the information
along with that received about the identity of the oil to determine
when the next oil change is required or to set values for
determining when a next oil change is required.
[0043] Accordingly the present invention provides a method of
operating such a machine comprising:
[0044] (i) using the detector to provide data about the identity of
the lubricating oil in the machine;
[0045] (ii) using at least one sensor to provide data which
indicates the state of the oil;
[0046] (iii) utilising the data obtained in (i) and (ii) to
determine when an oil change is required or to set values which can
be used to determine when an oil change is required.
[0047] A display may be coupled to machine management system or
electronic control unit and may indicate to the user the type of
oil present and when the next oil change is due.
[0048] In a preferred embodiment of the present invention, the
afore-mentioned machine is an engine.
[0049] According to another aspect of the present invention there
is provided a vehicle comprising an engine as described above and a
method of operating said vehicle.
[0050] According to another aspect of the present invention there
is provided a lubricating oil identification system comprising:
[0051] (i) a lubricating oil composition as described above;
and
[0052] (ii) a detector for detecting a passive marker in said oil
composition when the oil composition is in the machine.
[0053] The identification system may further comprise a machine
(e.g. an engine) as described above.
[0054] The present invention will be described in greater detail
with reference to the following examples. The present invention is,
however, not limited thereto.
EXAMPLE 1
[0055] In this example RFID chips are used as markers for a
lubricating oil. The RFID chip used was the Hitachi .mu.-chip
having dimensions of 0.4 mm by 0.4 mm by 0.22 mm (thick). The
Hitachi p-chip has a 128 bit read-only memory capable of storing
3.times.10.sup.38 unique identification numbers; it operates at
2.45 GHz (the same as Bluetooth); and it is a battery-less chip.
The detector is a p-Reader and is attached to the oil filter. It
can also be attached to the housing of the oil filter. Up to 10
Hitachi .mu.-chips are added per 4 litres of oil.
[0056] In operation a .mu.-chip is trapped in the oil filter; it
receives microwave power at a frequency of approximately 2.40-2.50
GHz from the .mu.-Reader; it generates electric power from the
microwave power; decodes its unique identification number and
transmits the data back to the .mu.-Reader. Software in the reader
alerts the user that a .mu.-chip has been detected and what its
identification number is. Reading distances of up to 30 cm are
achievable as are read response times of 20 ms.
EXAMPLE 2
[0057] This example demonstrates how an electronic nose can be
trained to distinguish between passenger car motor oil samples that
are fresh, heavily oxidised and contain an odourant marker.
[0058] The detector or electronic nose used in this example is a
commercially available electronic "nose" available under the trade
designation "Cyranose 320 Electronic Nose", manufactured by CYRANO
Sciences Incorporated. The particular model used was a multimeter
design and as such is not suitable for use in an engine. However,
the sensor array that actually detects the vapours is a small chip
which may be adapted for use in an engine. The chip comprises 32
individual thin-film carbon-black polymer composite chemiresistors
configured into an array. The sensor materials are thin films
deposited across two electrical leads on an alumina substrate,
creating the conducting chemiresistors. When the composite film is
exposed to a vapour-phase analyte, the polymer matrix acts like a
sponge and swells while absorbing the analyte. The increase in
volume causes an increase in resistance because the conductive
carbon-black pathways through the material are disrupted. When the
analyte is removed the polymer releases the analyte and shrinks to
its original size, restoring the conductive pathways. Each polymer
used in the array is chemically unique and absorbs the analyte
gases to a different degree. This creates a pattern of differential
response across the array. For a given lubricant, the sensor array
gives a unique "smell print".
[0059] Fresh oil samples were obtained from typical gasoline and
diesel engine oil formulations of differing viscosity grades, base
oil types and additive packages obtained from major lubricant
manufacturers.
[0060] In order to test how the electronic nose can be trained to
distinguish between passenger car motor oil samples that are fresh
and heavily oxidised, heavily oxidised oil samples were prepared by
the method disclosed at the 13.sup.th International Colloquium
Tribology, Esslingen, 15-17 Jan. 2002 by Shell Global Solutions
(UK), which comprises taking fresh oil samples and using a Shell
proprietary laboratory blown air oxidation rig in which the oils
were kept at 150.degree. C. and NO.sub.x in air was bubbled through
the oil at a prescribed rate so that oxidation conditions were
similar to those of the ASTM industry standard Sequence IIIE engine
test. In addition, a small amount of metal catalysts were added to
the lubricating oils to simulate typical wear metal concentrations
found in engine oil sumps.
[0061] The samples were subjected to these conditions for differing
periods of time, due to the fact that the oils oxidised at
different rates. In the laboratory test, the Total Base Number
(TBN), the Total Acid Number (TAN), and the viscosity increase was
monitored in order that it could be determined if the lubricant was
heavily oxidised or not.
[0062] This oxidised sample preparation was carried out by
utilising the publicly available commercial oxidised sample
preparation service that is advertised and available ex. Shell
Global Solutions (UK), Cheshire Innovation Park, P.O. Box 1,
Chester CH1 3SH, UK. (Email:
shellglobalsolutions@OPC.shell.com).
[0063] Oil samples containing odourant were prepared by
incorporating the odourant available under the trade designation
"Lemon Top" or the odourant available under the trade designation
"Ralley" (ex. Symrise (previously known as Dragoco)) into the
lubricating oil.
[0064] These oil samples were tested using the afore-mentioned
"Cyranose 320" multimeter. The experiment was set up as
follows:
[0065] Baseline purge: 30 secs; pump speed: medium
[0066] Sample draw: 90 secs; pump speed: medium
[0067] Sample draw 2: 0 secs
[0068] Snout removal: 0 secs
[0069] 1.sup.st sample gas purge: 0 secs
[0070] 1.sup.st air intake purge: 30 secs; pump speed: high
[0071] 2.sup.nd sample gas purge: 30 secs; pump speed: high
[0072] 2.sup.nd air intake purge: 30 secs; pump speed: high
[0073] Digital filtering: On
[0074] Substrate heater: On, 37.degree. C.
[0075] Training repeat count: 1
[0076] Identifying repeat count: 1
[0077] Active sensors: 05, 06, 23 and 31 switched off, all others
were on.
[0078] Algorithm: Canonical
[0079] Preprocessing: Auto-scaling
[0080] Normalisation: 1
[0081] Identification quality: Higher
[0082] The samples were prepared for testing as follows:
Approximately 4 ml of sample was transferred using a clean plastic
pastette into a 40 ml clean glass vial and sealed with PTFE-butyl
septum. The samples were then left in a 50.degree. C. oven for
one-and-a-half hours to allow the vapours to equilibrate in the
headspace. A G15 luer mount 9 cm stainless steel hypodermic needle
was attached to the nose to pierce the septum and draw the sample.
Another needle was used to vent the vial to ensure that the
pressure was equalised during the sample draw.
EXAMPLE 2A
[0083] The "Cyranose C320" multimeter was "trained" on ten
different samples of gasoline engine oils and their respective
completely oxidised forms. The training samples were tested at
random to make the training set as versatile as possible. The
canonical data for the training set is shown below in Table 1. All
the fresh oil data lies in the range of 2.8 to 5.9 for Factor 1,
whereas all the oxidised oil data lies in the range of -5.25 to
-2.2 for Factor 1. The two data sets are well separated and it is
clear that the fresh oils and heavily oxidised oils are easily
distinguishable.
[0084] Once the training set was validated using the
"cross-validation" option available on the "Cyranose C320"
multimeter, six "unknown" samples (A-F) were tested at random to
check that the "Cyranose C320" multimeter could identify them. All
of the unknown samples tested were correctly identified as being
fresh or completely oxidised.
[0085] Sensors 05, 06, 23 and 31 were switched off since earlier
investigations had identified that they gave erratic readings
during the first 10 to 20 seconds of the sample draw (it is thought
this is due to the possible presence of water vapour).
1TABLE 1 Sample No. Sample Details Factor 1 Factor 2 1 Fresh Shell
"Helix" Plus SAE-10W/40 2.8 0 2 Fresh Shell "Helix" Plus SAE-10W/40
5.9 0 3 Fresh Shell "Helix" Plus SAE-10W/40 3.6 0 4 Fresh Shell
"Helix" Plus SAE-10W/40 3.8 0 5 Fresh Shell "Helix" Plus SAE-10W/40
3.7 0 6 Fresh Shell "Helix" Plus SAE-10W/40 5.2 0 7 Fresh Shell
"Helix" Plus SAE-10W/40 3.8 0 8 Fresh Shell "Helix" Plus SAE-10W/40
4 0 9 Fresh Shell "Helix" Plus SAE-10W/40 4.1 0 10 Fresh Shell
"Helix" Plus SAE-10W/40 3 0 1a Fresh Shell "Helix" Plus SAE-10W/40
-5.25 0 oxidised for 196 hours in rig 2a Fresh Shell "Helix" Plus
SAE-10W/40 -5.2 0 oxidised for 196 hours in rig 3a Fresh Shell
"Helix" Plus SAE-10W/40 -3.2 0 oxidised for 196 hours in rig 4a
Fresh Shell "Helix" Plus SAE-10W/40 -4.3 0 oxidised for 196 hours
in rig 5a Fresh Shell "Helix" Plus SAE-10W/40 -3.1 0 oxidised for
196 hours in rig 6a Fresh Shell "Helix" Plus SAE-10W/40 -4.4 0
oxidised for 196 hours in rig 7a Fresh Shell "Helix" Plus
SAE-10W/40 -2.2 0 oxidised for 196 hours in rig 8a Fresh Shell
"Helix" Plus SAE-10W/40 -4.5 0 oxidised for 196 hours in rig 9a
Fresh Shell "Helix" Plus SAE-10W/40 -4.3 0 oxidised for 196 hours
in rig 10a Fresh Shell "Helix" Plus SAE-10W/40 -2.8 0 oxidised for
196 hours in rig N.B. "HELIX" is a Shell trade mark.
EXAMPLE 2b
[0086] A second set of experiments was carried out which included
fresh oils containing odourant molecules. The canonical plot for
this experiment is shown in Table 2. The fresh oil data lies in the
range of -3.3 to -8.5 for Factor 1 and in the range 0.75 to 4.0 for
Factor 2. The oxidised oil data lies in the range of -5.6 to -6.1
for Factor 1 and the range -0.9 to -3 for Factor 2. The fresh oil
with the added odourant lies in the range of 7 to 10.2 for Factor 1
and -1.8 to 0.1 for Factor 2. Again the three different data sets
are well separated.
[0087] Table 2 demonstrates that the sensor contained in the
"Cyranose C320 Electronic Nose" can distinguish fresh lubricant
from degraded lubricant, and can also distinguish fresh lubricant
from fresh lubricant containing an odourant.
2TABLE 2 Sample No. Sample Details Factor 1 Factor 2 1 Fresh Shell
"Helix" Plus SAE-10W/40 -3.3 3.7 2 Fresh Shell "Helix" Plus
SAE-10W/40 -1.8 3 3 Fresh Shell "Helix" Plus SAE-10W/40 -3 2.2 4
Fresh Shell "Helix" Plus SAE-10W/40 -0.85 4 5 Fresh Shell "Helix"
Plus SAE-10W/40 -1.7 0.75 1a Fresh Shell "Helix" Plus SAE-10W/40 -6
-2.1 oxidised for 196 hours in rig 2a Fresh Shell "Helix" Plus
SAE-10W/40 -6.1 -3 oxidised for 196 hours in rig 3a Fresh Shell
"Helix" Plus SAE-10W/40 -6 -0.9 oxidised for 196 hours in rig 4a
Fresh Shell "Helix" Plus SAE-10W/40 -5.8 -2.3 oxidised for 196
hours in rig 5a Fresh Shell "Helix" Plus SAE-10W/40 -5.6 -1.8
oxidised for 196 hours in rig 1b Fresh Shell "Helix" Plus
SAE-10W/40 10.2 -0.2 with 0.25% by volume Symrise "Lemon Top"
odourant added 2b Fresh Shell "Helix" Plus SAE-10W/40 7.25 -0.8
with 0.25% by volume Symrise "Lemon Top" odourant added 3b Fresh
Shell "Helix" Plus SAE-10W/40 7 -1.1 with 0.25% by volume Symrise
"Lemon Top" odourant added 4b Fresh Shell "Helix" Plus SAE-10W/40
7.25 0.1 with 0.25% by volume Symrise "Lemon Top" odourant added 5b
Fresh Shell "Helix" Plus SAE-10W/40 9.2 -1.8 with 0.25% by volume
Symrise "Lemon Top" odourant added
[0088] Table 3 shows the data for "smell print" for each of the
three types of oil (fresh, fresh +odourant, heavily oxidised). Each
of the three types of oil has a unique "smell print" which can be
recognised by the electronic nose. The data for each type of oil is
the maximum change in sensory output (arbitrary units) for each
sensor. Sensors 5, 6, 23 and 31 were switched off in these
experiments.
[0089] This example demonstrates how specific odourants can be
utilised as markers for oil and an electronic nose that utilises a
sensor array of the same type that is found in the "Cyranose 320"
Electronic Nose can be utilised as a detector in the identification
system of the present invention. The output from the sensor would
be (1) fresh oil +odourant (i.e. the specific type of oil could be
identified), (2) fresh oil without an odourant, or (3) heavily
oxidised oil. This output can be sent to the electronic management
system of the vehicle. If the signal (1) was received, the engine
management system can check whether the specific type of lubricant
identified was one that was approved by OEM. If signal (2) was
received, the engine management system can warn the user of the
vehicle that they should use an OEM approved lubricant. If signal
(3) is received by the engine management system, a light or other
warning mechanism can be used to advise the user that the lubricant
requires changing.
3TABLE 3 Oil with Odourant: Fresh Oil: Oxidised Oil: Shell "Helix"
Plus Shell "Helix" Shell "Helix" SAE-10W/40 with Plus SAE- Plus
SAE-10W/40 0.03 % by volume of 10W/40 oxidised for 196 Symrise
"Ralley" Sensor (Sensor output hours Odourant in in arbitrary
(Sensor output in (Sensor output in Array units) arbitrary units)
arbitrary units) 1 4072.5 36907.6 16344.0 2 4601.7 44224.9 17397.3
3 4009.7 42512.5 16033.3 4 2400.5 25036.7 10661.4 5 6 7 833.3
6342.7 2179.6 8 882.8 10033.1 5115.1 9 2501.0 33780.8 12644.7 10
177.6 1365.1 434.2 11 997.1 6014.3 2003.8 12 2849.2 40477.9 16134.7
13 560.0 5649.4 2331.8 14 1039.5 14060.4 7235.9 15 569.7 12273.2
2656.8 16 363.2 6736.5 2249.2 17 94.7 3085.0 743.1 18 1651.7
21180.4 11110.2 19 349.0 3721.5 1906.3 20 1771.7 35433.7 9891.2 21
192.9 3386.5 1150.3 22 288.6 1280.5 664.2 23 24 539.5 4161.1 2539.8
25 754.3 9665.9 2723.4 26 1628.3 18503.2 6398.5 27 1527.0 17988.9
14194.6 28 2859.1 31129.1 12856.2 29 4088.5 48187.4 17863.9 30
1114.9 9784.8 3703.6 31 32 1050.9 8934.6 5206.3
* * * * *