U.S. patent application number 11/400116 was filed with the patent office on 2006-08-10 for method and apparatus for measuring the color properties of fluids.
Invention is credited to Anthony Joseph Martino, Larry Eugene Steenhoek.
Application Number | 20060176484 11/400116 |
Document ID | / |
Family ID | 26793855 |
Filed Date | 2006-08-10 |
United States Patent
Application |
20060176484 |
Kind Code |
A1 |
Steenhoek; Larry Eugene ; et
al. |
August 10, 2006 |
Method and apparatus for measuring the color properties of
fluids
Abstract
An apparatus for inspection of fluids, particularly dispersions
and tints, having a fluid analysis cell with a cavity enclosed by
two light transmitting windows and having a spacer member fixedly
positioned therebetween which provides a fluid analysis chamber of
fixed pathlength where fluid flows by the windows and wherein the
flow is laminar and at a uniform shear to provide accurate color
measurements. The apparatus is particularly useful in the
manufacture of dispersions and tints used in the manufacture of
paints, so that the color of material being made can be accurately
matched to a standard color in the wet state with confidence that
the color will match in the dry state.
Inventors: |
Steenhoek; Larry Eugene;
(Wilmington, DE) ; Martino; Anthony Joseph; (West
Chester, PA) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
26793855 |
Appl. No.: |
11/400116 |
Filed: |
April 7, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10097999 |
Mar 13, 2002 |
7027147 |
|
|
11400116 |
Apr 7, 2006 |
|
|
|
60276991 |
Mar 19, 2001 |
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Current U.S.
Class: |
356/413 |
Current CPC
Class: |
G01N 21/05 20130101;
G01N 21/251 20130101; G01N 2021/0346 20130101; G01N 2021/058
20130101 |
Class at
Publication: |
356/413 |
International
Class: |
G01N 21/25 20060101
G01N021/25 |
Claims
1. A method of measuring a color property of a wet fluid comprising
supplying a sample volume of liquid to a transmission cell,
allowing the fluid to pass through the cell at a fixed pathlength
and zero bypass through two viewing windows enclosing each end of
the cell, and measuring the color property of the sample volume by
light transmittance while the sample is flowing in the cell.
2. The method of claim 1 in which the flow of the sample is
unidirectional and laminar.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. .sctn.119
from U.S. application Ser. No. 10/097,999, filed Mar. 13, 2002,
which claims the benefit of Provisional Application Ser. No.
60/276,991, filed Mar. 19, 2001, which is incorporated by reference
herein for all purposes as if fully set forth.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a method of and apparatus for the
inspection of fluids. In particular, the invention relates to an
improved apparatus for measuring the color properties, in
transmission, of fluids, such as pigment dispersions and tints
flowing through the apparatus.
[0003] Pigment dispersions and tints are widely used nowadays in
formulating high performance coating compositions used in
particular for exterior finishes for automobiles and trucks.
[0004] In the manufacture of such dispersions and tints, one
problem is to measure the color and strength of the material as it
is being made, so that adjustments can be quickly made to bring
this material within acceptable color tolerance values. Color
measurements nowadays are carried out by a manual process, which
involves taking an aliquot of the material, blending it with a
standard white or black paint, spraying out the blends as a coating
onto panels, baking and drying the panels, and then measuring one
or more color properties of the dried coating using a colorimeter
or spectrophotometer against a standard. Adjustments are then made
to the batch until the color parameters match those of the
standard.
[0005] Color measurements by this method are very time consuming
because of sample preparation and drying times. Also, this
procedure may have to be repeated numerous times before the desired
color property is achieved. Another problem which arises with this
procedure is that the accuracy of the test is dependent on the
color and strength stability of the standard white or black paints.
Even with careful control, these standards tend to vary from batch
to batch and also tend to flocculate or settle in time, leading to
poor test repeatability and making it very difficult to accurately
analyze the color and strength of the batch as it is being
made.
[0006] The aim within the industry for some time has been to
measure the color properties of these fluids in a wet state and in
a way which predicts the color of the fluid when applied and dried.
The primary benefits are mainly associated with time savings
although some are associated with the increased likelihood of an
automated manufacturing process.
[0007] Conventional spectrophotometers, employing cuvette-type
sample chambers, have been proposed to make such wet measurements
by measuring a transmission spectrum of a wet transparent sample.
Simply taking a sample of wet fluid and putting it in a glass cell
and measuring its color properties generally leads to inconsistent
results, mostly due to poor repeatability and operator variability.
In addition, cell pathlengths in such spectrophotometers are, in
general, too large for such measurements. Moreover, settling and
flocculation can also occur, changing the color of the sample and
producing erroneous results.
[0008] Another instrument, described in Batista et al. WO 98/16822,
published Apr. 23, 1998, employing a variable pathlength fluid
measurement cell to measure properties of fluids, including color,
could be used for such measurements. However, this equipment
possesses multiple moving parts which are part of the fluid path,
which causes difficulty in cleaning, and are difficult to maintain.
Another disadvantage is that the design is such that it requires a
high volume of fluid sample to take proper readings.
[0009] Therefore, there is still a need to provide a method and
apparatus for color measurement of wet fluids that: produces
acceptably consistent results; does not require the spraying and
blending with white or black standards and the production of a
number of dry samples; cleans rapidly (within 1 or 2 minutes) so
that the cycle time of the measurement is extremely small compared
to process changes; and predicts with confidence that the wet
readings will also match the standard in the dry.
[0010] In addition to the above features, there is also a need to
provide a method and apparatus that automatically delivers sample
to the analysis cell so that said apparatus could be easily
connected to a process stream on-line for measurement and control
of process color and strength; and is intrinsically safe, so that
it can be placed on a plant floor in an environment wherein may be
contained an explosive atmosphere.
SUMMARY OF THE INVENTION
[0011] An apparatus for inspection of fluids having the following
components:
[0012] a fluid analysis cell having a cavity therein for measuring
light transmittance of a sample;
[0013] an upper and lower light transmitting window enclosing
opposite ends of the cavity;
[0014] a spacer fixedly positioned in said cavity between said
upper and lower viewing windows providing a fluid chamber where
fluid flows between said windows;
[0015] inlet and outlet channels connected in fluid communication
with said fluid chamber to enable fluid to flow into and out of
said fluid chamber, the flow of fluid through the chamber
preferably being unidirectional laminar flow at uniform shear;
and,
[0016] a light source and a spectrophotometer, preferably a single
beam spectrophotometer, associated with the cell to measure color
parameters of the fluid passing through the viewing window by
transmittance.
[0017] The inspection apparatus also preferably includes the
following components:
[0018] a camera lens to interface with the spectrophotometer to
gather light from diffuse as well as specular directions;
[0019] a purged explosion-proof enclosure for containing all
electrical/electronic components, as well as the light source for
the instrument;
[0020] an automatic pneumatically-controlled sample system for
delivery of the sample to the fluid analysis chamber; and, an
explosion-proof pump for high pressure delivery of cleaning solvent
to the fluid analysis chamber for rapid cleaning of said
chamber.
[0021] A method for measuring the color properties of a fluid using
the above apparatus is also a part of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a front view of the apparatus in accordance with
the invention.
[0023] FIG. 2 is a rear view of the apparatus of FIG. 1.
[0024] FIG. 3A is a side view of the flow-through fluid analysis
cell used in the apparatus of FIG. 1.
[0025] FIG. 3B is an isometric view of the flow-through fluid
analysis cell of FIG. 3A.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] In general, the apparatus of the invention can be used to
inspect a wide variety of fluids (such as dispersions, tints, inks,
paints, and etc.) but is designed particularly to measure the color
properties of dispersions and tints that are used in the
manufacture of high performance automotive coatings. The apparatus
is specifically designed to measure the color properties of the
fluids flowing through the apparatus using wet light transmittance
measurements over the visible spectrum in a way that produces
accurate instrumental readings.
[0027] Referring now to FIGS. 1 and 2 of the drawings, the
apparatus according to the invention comprises a housing 10 which
contains an optical unit 12, for providing a source of visible
light to a fluid analysis unit 14 and for detecting the visible
light emitted therefrom. Both the optical unit 12 and fluid
analysis unit 14 are connected to a system control unit, preferably
a computer, 16 for data acquisition, spectral analysis, and control
of the functions of units 12 and 14.
[0028] The optical unit 12 preferably consists of a monochromator
18 and a photodiode array detector 20, together in essence
comprising a single beam spectrophotometer, having a single input
22 for detecting light over the visible spectrum, from 400 nm to
700 nm, typically in 10 nm increments. The photodiode array is
controlled by a controller unit 24 interfaced with the system
control unit 16, preferably via an optical RS-232 interface
contained therein utilizing a fiber optic cable 25. Light is
provided to input 22 from a light source 26 preferably consisting
of an incandescent halogen lamp (not shown), e.g., a tungsten
halogen lamp, that emits light over a range of wavelengths from 400
to 700 nanometers (nm). The lamp is contained in a housing 28 and
powered by a standard power supply 30. The light output from the
lamp is preferably collimated.
[0029] The transmitted light beam, after passing through the fluid
analysis unit 14, is directed through a shutter 32. The shutter is
used to block the light emitted from the light source, so that
dark-current measurements can be made during the calibration step.
The transmitted light is then received by a camera lens 34 and
passed through the monochromator 18 to the detector 20. The
entrance and exit slits (not shown) of the monochromator enable the
detector to detect single frequency radiation and, the size of the
slits, together with the diode spacing of the diode array detector,
defines the wavelength resolution of the spectrophotometer.
[0030] The lamp housing 28 also preferably includes photometric
filters (not shown) contained in a filter holder 36 to vary the
intensity of light reaching the detector. This enables the detector
to operate in its optimum condition, without saturation by high
intensity light, or lack of resolution with low intensity light,
which enables the detectors to see virtually in the dark. The
detector 20 is preferably a standard photodiode array detector
which comprises a high sensitivity photodiode array connected to a
low noise amplifier. The transmitted light is sent to the detector
for spectral measurement and the detector signal is then fed via
fiber optic RS-232 cables 25 from the diode array controller 24 to
a computer 16 for spectral analysis and L*, a*, b* color value
computation, which constitutes the color measurement.
[0031] The apparatus may also contain an integrating sphere (not
shown) integral with the light source for diffuse illumination of
the sample, in the case where the measured fluid possesses more
than negligible light scattering capability. Said integrating
sphere may also possess an automatically controlled black trap and
white reflector sliding mechanism (not shown) for illuminating the
sample with either solely diffuse light or diffuse and specular
light for analysis of samples possessing scatterers.
[0032] Fluid analysis unit 14, comprises a fluid control unit 38,
as will be later described, which supplies a continuous flow of
fluid under investigation or reference fluid to a flow through
fluid analysis cell 40.
[0033] Referring now to FIGS. 3A and 3B, the fluid analysis cell 40
is designed to provide a fluid stream of uniform color so that
accurate color measurements can be made. The cell 40 comprises a
vessel containing upper and lower viewing widows 42 and 44,
respectively, preferably cylindrical windows, that are fixedly
mounted to each other and close the opposite ends of the vessel.
The viewing widows are made of materials that are transparent to
visible light, for example such as borosilicate glass, quartz, or
sapphire, and allow for light transmission through the cell.
Between the windows is a cavity which forms a fluid analysis
chamber 46. The fluid analysis chamber 46 is formed by having a
spacer member 48, such as a brass shim, inserted between the
viewing windows.
[0034] The spacer member 48 is provided with an rectangular cavity
50 which creates a fluid flow channel 52 therein. The thickness of
the spacer determines the cell pathlength, and may be of any size,
although for practical reasons (because of absorbance of the
samples being measured) a thickness between 1 and 10 mils (0.001 to
0.010 inch) is usually chosen. The upper and lower viewing windows
and shim 48 are fixedly held in place by upper and lower flanges 54
and 56 bolted together to hold the entire assembly. Elastomeric
gaskets 58 and 60 are inserted respectively between upper flange 54
and upper window 42 and between lower flange 56 and lower window 44
to seal the assembly. The flanges 54 and 56 are similarly provided
with flow conduits 62 and 64, respectively, to enable fluid
communication with the flow channel 52 and provide fluid inlet and
outlet channels 66 and 68 to the cell. The fluid inlet and outlet
channel are usually threaded to receive standard fittings (not
shown) to interface with inlet and outlet pipes (not shown).
[0035] The components that are used to form the transmission cell
40 should be made of materials which are non-reactive with the
fluid that is being passed through the apparatus. Typically the
structural components are made of brass or stainless steel and the
viewing windows are made of borosilicate glass, quartz, or
sapphire, as indicated above. The viewing windows may also be
coated with a fluorocarbon polymer to prevent fluid residue
build-up on the cell.
[0036] The transmission cell 40 of the present invention may be
characterized as a zero bypass cell, which means that all fluid
entering is exposed to the viewing windows. Zero bypass enables
sample to flow through the cell at a uniform shear to provide a
constant interface that can be measured and at a sufficient
velocity to prevent a build-up on the cell window. Flow through the
cell should also be laminar which prevents settling or flocculation
of any pigment suspended in the fluid. Laminar flow also provides a
sample of uniform color in the viewing area to insure uniform color
measurements. The zero bypass cell also guarantees that all of the
fluid will cross the optical view path so as to give a true sample
of the fluid.
[0037] Another feature of the cell used in the present invention is
that the pathlength of light through the sample is fixed but can be
set manually by a change in the shim spacer in the cell. Thus one
always knows what the pathlength is and does not have to worry
about pathlength control and errors that can result during
measurement. Pathlength of the light through the sample is set
small enough to allow sufficient light throughput to be accurately
measured by the instrument detectors, yet large enough to avoid
saturation of the detectors. This enables measurement of
transparent as well as opaque fluids. Additionally, the pathlength
should be set so that the appropriate lightness of the sample is
attained, such that possible colorant modification, or shading, in
the wet state corresponds to that in the dry. As indicated above,
the pathlength is typically set between 1 and 10 mils. However, for
some optically dense dispersions, dilution may be necessary to
obtain full spectral information.
[0038] To maintain proper pathlength control, temperature of the
measurement cell and the liquid within the cell is preferably held
to a narrow enough range (e.g., plus or minus 5.degree. C.) such
that thermal expansion does not change the effective pathlength and
such that the standard and sample readings are comparable.
Temperature control in the present invention is preferably provided
by a thermoelectric cooler 70 disposed in the housing 10 next to
the cell to insure a constant temperature of fluid passing through
the cell, as shown in FIG. 2. The test sample and liquid standard
should also be measured at the same temperature within this range
to insure uniformity.
[0039] The fluid flow control unit, or sample system, 38 is also
shown in FIG. 2. Generally any type of control unit can be provided
which pumps fluid at a uniform velocity into the apparatus through
the inlet and into the fluid chamber formed by the spacer and
across the viewing windows and out through the outlet. Color
measurements can then be made through the windows by transmittance
as a sample volume of fluid is passing through the cell.
[0040] In the preferred embodiment as shown, the fluid control unit
or sample system 38 provides for injection of sample into the cell
through a sample injection port 72 and for sample line and cell
cleanout. The fluid control unit itself is preferably controlled by
the same computer 16 which controls the optical unit which gathers
the spectral measurements. This can be accomplished via an RS-232
serial link 74 through an input/output (I/O) rack 76 (e.g. a
programmable logic controller or PLC), which in turn triggers
solenoid valves 78, releasing air to the pneumatic components (not
shown) of the sample system. Additional I/O rack modules 80 are
preferably interfaced to pumps, temperature and pressure sensors,
and purge air supply (all not shown).
[0041] Preferably, the system possesses an explosion-proof NEMA 4
enclosure 10 for all electrical and electronic components as well
as the light source. Said enclosure is also purged with air to a
pressure super-ambient with respect to the exterior environment to
prevent buildup of an explosive atmosphere, possibly present
exterior to the enclosure, within the enclosure. The purge air
system consists of an air purge unit 82 plus a pressure vessel air
tank 84 for containment of an emergency air purge in event of
system failure as shown in FIGS. 1 and 2.
[0042] The air purge unit contains an electronic control unit 86
which controls all electrical power to the system, and has sensors
capable of detecting a breach of the cabinet seal, whereupon an
emergency electrical shutdown of the system is effected, along with
a controlled depressurization of the emergency air tank and venting
of the air via a conduit (not shown) through the light source
housing 28, thus preventing any possible explosive vapors from
coming in contact with the light source until it is cooled down.
Additionally, the electronic control unit will not allow startup of
the system until a timed fast purge of the enclosure via a conduit
(not shown) is first accomplished. Moreover, a pressure sensor (not
shown) on the emergency air tank acts as a trigger for startup of
the light source, disabling the same until the air tank is at full
pressure.
[0043] Before a fluid sample may be measured, a reference reading
is taken by first injecting solvent into the sample cell 40 via a
standard menu-driven computer program. The program controls the
sample system's 38 pneumatic components (not shown) by signaling
the I/O rack 76 via RS-232 serial link 74 to operate the
appropriate component via solenoid valves 78 in the cabinet 10.
When each task is completed (by time or sequence), the pneumatic
components return to their default positions.
[0044] To take a reference spectrum, the computer-controlled sample
system's pneumatic components (not shown) are set such that solvent
from the solvent reservoir (not shown) is directed by a pump 88
into the sample cell 40. A dark current spectrum is taken by
blocking the light with the air-operated shutter 32 inside the
cabinet (this happens each time a spectrum is collected for both
reference and sample measurements). Once this has been recorded by
the program, the shutter is opened and the program reads and
records the light spectrum from the diode array 20, subtracts the
dark current spectrum from reference and stores the result in raw
format as the reference spectrum.
[0045] When a fluid sample is to be analyzed, a sample is delivered
to the sample system 38, either manually or automatically. The
sample system is set to air-drive the sample through the sample
cell 40. The computer program reads and records the light spectrum
from the diode array 20 and converts it into transmission by
comparing it with the solvent reference spectrum as well as the
dark current reading from the diode array. L*, a*, and b* are then
calculated via standard equations.
[0046] The color technology used for spectral analysis, calculation
of the L*, a*, b* color values of the fluid being tested therefrom,
and making color comparisons to a standard is well known and fully
described in Falcoff et al, U.S. Pat. No. 4,403,866 issued Sep. 13,
1983, hereby incorporated by reference.
[0047] To clean the sample system 38, the system is set in such a
way that solvent is directed from the reservoir (not shown) through
the sample system first, to effect cleaning there, and then through
the cell 40, wherein the high shear of the solvent flow cleans the
faces of the cell windows. All pneumatic components then return to
their default positions when the operation is complete, and the
system is ready for the next sample.
[0048] The apparatus can be used in a variety of chemical processes
in which color of the resulting product is measured. It is
preferably used in a paint, pigment dispersion, inkjet ink,
printing ink, or tint manufacturing process. The apparatus of this
invention can be positioned at a remote location from the
manufacturing process for either at-line or off-line testing, or
can be and preferably is connected to the production unit for
on-line color testing of the wet fluid as it is being made.
Allowing the fluid to flow through the cell directly from the
processing unit allows for on-line or continuous testing and
enables fully automated batch or continuous manufacture of the
fluid. The total cycle time of the apparatus as shown in FIG. 1 is
a few minutes as opposed to hours using conventional equipment.
Moreover, it has been found that in making color measurements using
this apparatus, there is a good correlation between the color
properties of the wet fluid and dry fluid, which enables visually
accurate color matches to be achieved.
[0049] A variation of this invention is to use a colorimeter in
place of the spectrophotometer.
* * * * *