U.S. patent application number 10/286149 was filed with the patent office on 2003-03-27 for methods for identification and verification.
Invention is credited to Kaiser, Bruce J., Kenning, Don, Kuhlman, Robert D., Schoepflin, Dan, Starks, Lloyd, Watson, David J..
Application Number | 20030058990 10/286149 |
Document ID | / |
Family ID | 24878770 |
Filed Date | 2003-03-27 |
United States Patent
Application |
20030058990 |
Kind Code |
A1 |
Kaiser, Bruce J. ; et
al. |
March 27, 2003 |
Methods for identification and verification
Abstract
An apparatus and method in which one or more taggants that are
intrinsically located--or extrinsically placed--in an article or
product, such as carpet. The taggants are detected by x-ray
fluorescence analysis to identify or verify the article or its
point of manufacture. The taggants are manufactured as part of the
article or the taggant is placed into a coating, label, or
otherwise embedded within the article for the purpose of later
verifying the presence or absence of these elements by x-ray
fluorescence, thus determining the unique elemental composition of
the taggant within the article.
Inventors: |
Kaiser, Bruce J.; (St.
Louis, MO) ; Starks, Lloyd; (Dalton, GA) ;
Watson, David J.; (Richland, WA) ; Kenning, Don;
(Kennewick, WA) ; Schoepflin, Dan; (Richland,
WA) ; Kuhlman, Robert D.; (Richland, WA) |
Correspondence
Address: |
KENNETH E. HORTON
RADER, FISHMAN & GRAUER PLLC
RIVERPARK CORPORATE CENTER ONE
10653 SOUTH RIVERFRONT PARKWAY, SUITE 150
SOUTH JORDAN
UT
84095
US
|
Family ID: |
24878770 |
Appl. No.: |
10/286149 |
Filed: |
November 1, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10286149 |
Nov 1, 2002 |
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09716625 |
Nov 20, 2000 |
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6477227 |
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Current U.S.
Class: |
378/45 |
Current CPC
Class: |
G01N 23/223 20130101;
G01N 2223/076 20130101 |
Class at
Publication: |
378/45 |
International
Class: |
G01T 001/36 |
Claims
We claim:
1. A method for controlling the quality of a process, comprising:
providing a process having at least one range of operation;
incorporating a taggant into the process to trace the at least one
range; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
2. The method of claim 1, further including modifying the process
if the process does not operate within the at least one range.
3. The method of claim 1, the process coating a protective film on
a carpet.
4. An article made by a method for controlling the quality of a
process, comprising: providing a process having at least one range
of operation; incorporating a taggant into the process to trace the
at least one range; causing the taggant to radiate at least one
x-ray and analyzing whether the at least one x-ray has a specific
energy; and determining whether the process operates within the at
least one range.
5. A method for controlling the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; incorporating a taggant into the process to trace
the at least one characteristic; causing the taggant to radiate at
least one x-ray and analyzing whether the at least one x-ray has a
specific energy; and determining whether the article exhibits the
at least one characteristic.
6. The method of claim 5, further including modifying the process
if the article does not exhibit the at least one
characteristic.
7. The method of claim 5, the process coating a protective film on
a carpet.
8. An article made by the method for controlling the quality of an
article, comprising: providing a process for making an article
having at least one characteristic; incorporating a taggant into
the process to trace the at least one characteristic; causing the
taggant to radiate at least one x-ray and analyzing whether the at
least one x-ray has a specific energy; and determining whether the
article exhibits the at least one characteristic.
9. A method for measuring the quality of a process, comprising:
providing a process having at least one range of operation;
incorporating a taggant into the process to trace the at least one
range; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
10. The method of claim 9, the process coating a protective film on
a carpet.
11. A method for measuring the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; incorporating a taggant into the process to trace
the at least one characteristic; causing the taggant to radiate at
least one x-ray and analyzing whether the at least one x-ray has a
specific energy; and determining whether the article exhibits the
at least one characteristic.
12. The method of claim 11, the process coating a protective film
on a carpet.
13. A method for monitoring the quality of a process, comprising:
providing a process having at least one range of operation;
incorporating a taggant into the process to trace the at least one
range; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
14. The method of claim 13, the process coating a protective film
on a carpet.
15. A method for monitoring the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; incorporating a taggant into the process to trace
the at least one characteristic; causing the taggant to radiate at
least one x-ray and analyzing whether the at least one x-ray has a
specific energy; and determining whether the article exhibits the
at least one characteristic.
16. The method of claim 15, the process coating a protective film
on a carpet.
17. A method for controlling the quality of a process, comprising:
providing a process with a taggant to trace at least one range of
operation; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
18. The method of claim 17, further including modifying the process
if the process does not operate within the at least one range.
19. An article made by a method for controlling the quality of a
process, comprising: providing a process with a taggant to trace at
least one range of operation; causing the taggant to radiate at
least one x-ray and analyzing whether the at least one x-ray has a
specific energy; and determining whether the process operates
within the at least one range.
20. A method for controlling the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; the process having a taggant to trace the at least
one characteristic; causing the taggant to radiate at least one
x-ray and analyzing whether the at least one x-ray has a specific
energy; and determining whether the article exhibits the at least
one characteristic.
21. The method of claim 20, further including modifying the process
if the article does not exhibit the at least one
characteristic.
22. An article made by the method for controlling the quality of an
article, comprising: providing a process for making an article
having at least one characteristic; the process having a taggant to
trace the at least one characteristic; causing the taggant to
radiate at least one x-ray and analyzing whether the at least one
x-ray has a specific energy; and determining whether the article
exhibits the at least one characteristic.
23. A method for measuring the quality of a process, comprising:
providing a process with a taggant to trace at least one range of
operation; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
24. A method for measuring the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; the process having a taggant to trace the at least
one characteristic; causing the taggant to radiate at least one
x-ray and analyzing whether the at least one x-ray has a specific
energy; and determining whether the article exhibits the at least
one characteristic.
25. A method for monitoring the quality of a process, comprising:
providing a process with a taggant to trace at least one range of
operation; causing the taggant to radiate at least one x-ray and
analyzing whether the at least one x-ray has a specific energy; and
determining whether the process operates within the at least one
range.
26. A method for monitoring the quality of an article, comprising:
providing a process for making an article having at least one
characteristic; the process having a taggant to trace the at least
one characteristic; causing the taggant to radiate at least one
x-ray and analyzing whether the at least one x-ray has a specific
energy; and determining whether the article exhibits the at least
one characteristic.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to apparatus and
methods for identification and verification. More particularly, the
present invention relates to apparatus and methods for detecting an
element or compound intrinsically present--extrinsically added--in
an article or product by using X-ray fluorescence to identify and
verify that article or product. Even more particularly, the present
invention related to apparatus and methods for controlling the
quality of a manufacturing process and the resulting product by
using XRF analysis.
BACKGROUND OF THE INVENTION
[0002] There has been significant interest in apparatus and methods
for identifying and verifying various articles or products such as
explosives, ammunition, paint, petroleum products, and documents.
Known methods used to identify and verify generally involve adding
and detecting materials like code-bearing microparticles, bulk
chemical substances, and radioactive substances. Other methods used
for identifying and verifying articles include those described in
U.S. Pat. Nos. 6,030,657, 6,024,200, 6,007,744, 6,005,915,
5,849,590, 5,760,394, 5,677,187, 5,474,937, 5,301,044, 5,208,630,
5,057,268, 4,862,143, 4,390,452, 4,363,965, and 4,045,676, as well
as European Patent Application Nos. 0911626 and 0911627, the
disclosures of which are incorporated herein by reference.
[0003] It is also known to apply materials to articles in order to
track, for example, point of origin, authenticity, and their
distribution. In one method, inks which are transparent in visible
light are sometimes applied to materials and the presence (or
absence) of the ink is revealed by ultraviolet or infrared
fluorescence. Other methods include implanting microscopic
additives which can be detected optically. However, detecting these
materials is primarily based on optical or photometric
measurements.
[0004] Unfortunately, many of the apparatus and methods for
identifying and verifying articles using such materials (called
taggants) are unsatisfactory for several reasons. First, they are
often difficult and time-consuming. In many instances, a sample of
the article must be sent to an off-site laboratory for analysis. In
other instances, the apparatus are often expensive, large, and
difficult to operate. In yet other instances, the taggant used is
radioactive, causing serious health concerns.
[0005] The known apparatus and methods for identification and
verification are also unsatisfactory because they require a
"line-of-sight" analysis method. This line of sight requirement
entails that the apparatus must be able to "see" the taggant in
order to detect it. This can be detracting when it would be
desirable to detect the taggant without having to see the taggant,
e.g., such as when the taggant is located in the middle of large
package with packaging and labels "covering" the taggant.
SUMMARY OF THE INVENTION
[0006] The present invention provides an apparatus and method in
which one or more taggants that are intrinsically located--or
extrinsically placed--in an article or product are detected by
x-ray fluorescence analysis to identify or verify the article or
its point of manufacture. The taggants are manufactured as part of
the article or the taggant is placed into a coating, packaging,
label, or otherwise embedded within the article for the purpose of
later verifying the presence or absence of these elements by x-ray
fluorescence to determine the unique elemental composition of the
taggant within these articles.
[0007] By using x-ray fluorescence analysis, the apparatus and
methods of the present invention are simple and easy to use, as
well as provide detection by a non line-of-sight method to
establish the origin of materials, point of manufacture,
authenticity, verification, or product security. The present
invention is extremely advantageous because it is difficult to
replicate, simulate, alter, transpose, or tamper. Further, it is
easily recognizable by a user in either overt or covert form,
verifiable by a manufacturer or issuer, and is easily applicable to
various forms of media in the articles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIGS. 1, 2a, 2b, 3, 4a, 4b, and 5-8 are views of apparatus
and methods for identification and verification according to the
present invention.
[0009] FIGS. 1, 2a, 2b, 3, 4a, 4b, and 5-8 presented in conjunction
with this description are views of only particular--rather than
complete--portions of apparatus and methods for identification and
verification.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The following description provides specific details in order
to provide a thorough understanding of the present invention. The
skilled artisan would understand, however, that the present
invention can be practiced without employing these specific
details. Indeed, the present invention can be practiced by
modifying the illustrated apparatus and method and can be used in
conjunction with apparatus and techniques conventionally used in
the industry. For example, the present invention is described with
respect to a manufacturing process for making carpets. But a
skilled artisan could easily adapt the present invention for other
manufacturing processes and other products, such as plastic
materials.
[0011] The present invention uses x-ray fluorescence analysis to
detect at least one taggant which is intrinsically or extrinsically
present in the material of a product or article. With x-ray
fluorescence (XRF) analysis, x-rays produced from electron shifts
in the inner shell(s) of atoms of the taggants and, therefore, are
not affected by the form (chemical bonding) of the article being
analyzed. The x-rays emitted from each element bear a specific and
unique spectral signature, allowing one to determine whether that
specific taggant is present in the product or article.
[0012] FIGS. 1, 2a, and 2b represent how it is believed XRF
generally operates. In FIG. 1, primary gamma rays or x-rays 40 are
irradiated on a sample of a target material 46 of article 42.
Secondary x-rays 44 are emitted from that sample of target material
46.
[0013] In FIGS. 2a and 2b, atom 48 of a taggant located within
target material 46 has nucleus 50 surrounded by electrons 52 at
discrete distances from nucleus 50 (called electron shells). Each
electron shell has a binding energy level equal to the amount of
energy required to remove that electron from its corresponding
shell. The innermost shell is the K shell, and has the highest
binding energy level associated with it. Electron 54 is located
within K shell 56.
[0014] Primary x-ray or gamma ray photon 40 impacting atom 48 has a
given energy. If that energy is greater than the binding energy
level of K shell 56, the energy of x-ray photon 40 is absorbed by
atom 48, and one of the electrons in K shell 56 (i.e., electron 54)
is ejected. With a vacancy now in K shell 56 left by electron 54,
atom 48 is energetic and unstable. To become more stable, that
vacancy in K shell 56 can be--and usually is--filled by an electron
located in a shell with a lower binding energy level, such as
L-shell electron 58 in L shell 60. As L-shell electron 58 fills the
vacancy in K shell 56, atom 48 emits a secondary x-ray photon 44.
The energy levels (or corresponding wavelengths) of such secondary
x-ray photons are uniquely characteristic to each taggant, allowing
the presence or absence of any specific taggant to be
determined.
[0015] The at least one taggant can be intrinsically or
extrinsically present in the product to be detected (the "target
material"). When the taggant(s) is intrinsically present, it is a
component (either as an element, compound, or other type of
composition) in at least one portion of that target material. When
the taggant(s) is extrinsically present, it can be added,
incorporated, or inserted into the target material as described
below.
[0016] The at least one taggant employed in the present invention
can be any suitable taggant known in the art. See, for example,
U.S. Pat. Nos. 5,474,937, 5,760,394, and 6,025,200, the disclosures
of which are incorporated herein by reference. Suitable taggants
include any element or compound which is capable of being detected
via XRF. The type of elements that can be used as the taggant are
theoretically any of those listed in the periodic table, but the
lower energy emitted by electrons in the lower atomic-number
elements could be a limiting factor. Such lower energies can be
re-absorbed much easier into its own material matrix or, in some
cases, into the ambient atmosphere (e.g, air). Further, different
isotopes of an element, as well as elements which "excite" only
under certain conditions--such as specific temperature
ranges--could be employed as the taggant in the present invention.
Example of taggants that could be used in the present invention
include any element with an atomic number ranging from 6 to 94.
Preferably, any element above iron on the periodic element, yet
within the above range, can be used as the at least one taggant in
the present invention. More preferably, any transition elements
between germanium and silver can be used as the at least one
taggant in the present invention.
[0017] The type of taggant depends, among other things, on the
target material in which it is located. The target material can
interfere with the XRF detection because, as described below,
backscattering and peaks emitted by the composition of the target
material during XRF analysis can interfere with the taggant peaks.
For example, if paper contained an As taggant and trace amounts of
Pb existed in the paper, the K-level electrons of As and L-level
electrons of Pb could give confusing readings during XRF
detection.
[0018] In one aspect of the invention, the type of taggant should
be selected based on the ability of the taggant and/or the
substance in which it is located (i.e., a coating) to attach or
bond to the target material. In many instances, the target material
will be used, handled, and/or washed extensively. If the taggant
(or the substance in which is located) is removed from the target
material under such conditions, tagging the target material is of
little value. For example, if a film or coating (e.g., ink)
containing a taggant is applied to a target material (e.g., paper),
the taggant and coating should be selected so that they will not be
removed by the conditions to which the target material is
periodically subjected (e.g., extensive contact with hands).
Preferably, the coating and/or the taggant is selected in this
aspect of the invention so that it chemically attaches or bonds to
the target material, like paint attaches and bonds with a wall.
[0019] In another aspect of the invention, the type of taggant can
be selected based on the ability of the taggant and/or the
substance in which it is located (i.e., a coating) to be removed
from the target material. In many instances, the purpose for which
the target material is tagged will be temporary. After this purpose
is completed, the taggant is no longer needed and can optionally be
removed. For example, if an identifying film or coating containing
a taggant is applied to a target material, once the target material
has been identified, the identifying film of coating may no longer
be needed and can be removed by suitable means. Preferably, the
coating and/or the taggant is selected in this aspect of the
invention so that it is removable by mechanical or chemical
means.
[0020] The amount and concentration of the taggant in the target
material can also vary depending on the number of elements used and
energy needed. The amount of taggant employed in the present
invention is determined by the minimum amount needed for XRF
detection. Additional amounts of taggant can be used as described
below. The concentration of the taggant is at least about 1 part
per million (ppm), and can range from about 1-100 ppm. Larger
taggant amounts can be used, but for economic reasons, a small
amount is sufficient. Even lower taggant concentrations can be used
(i.e., less than 1 ppm) as improved XRF devices and techniques
become available.
[0021] The form of the taggant in the target material can also
vary. The form can be any compound (i.e., salt) or molecule--either
small or large--containing the element that is added by itself or
with other components. Indeed, the taggant can be combined with
various components and/or additives to make a mixture and/or
solution. These other components or additives can be selected for
various purposes, e.g., to modify the XRF properties, to modify the
ability to be inserted into an article/product, to stabilize the
mixture or solution, or other purpose known in the chemical
arts.
[0022] In one aspect of the invention, the at least one taggant is
a combination or plurality of taggants. A plurality of taggants
could include more than one taggant of the same type, e.g., the
same element or compound. A combination of taggants could also be
more than one type of taggant, e.g., a different element or
compound in different media. For example, a taggant dispersed in
ink which has been placed on paper which also contains the same or
different taggant. The plurality of taggants could also include a
combination of at least one intrinsic and at least one extrinsic
taggant.
[0023] The at least one taggant incorporated in the target material
can provide a distinctive code. Such a code could be based on the
number and types of taggants present or absent, an abundance ratio
(i.e., concentrations) of the same or different taggants, the
location of the taggants within the material (i.e., a barcode made
of a series of taggants with a space, where the space could be part
of the code), the presence of multiple types or forms of a single
taggant, or a combination thereof.
[0024] As one example of such a code, the present invention can
include a system in which the concentration of one taggant in a
targeted material is controlled to provide a distinctive code. For
example, for tagging ten commercially prepared batches of
carpeting, the taggant yttrium oxide can be used. Ten unique codes
could then be created for these ten batches by preparing samples of
the target material containing various concentrations (i.e., 10
ppm, 20 ppm, . . . 100 ppm) of that taggant.
[0025] The number of unique codes available with the use of just a
single taggant depends on the precision with which that
concentration can be controlled and measured in the sample. For
example, if techniques allow concentrations in about 10 ppm
increments, 10 unique codes (i.e., 10 ppm, 20 ppm, . . . 100 ppm)
can readily be constructed from a single taggant for that
concentration range. Additional codes could be created for larger
concentration ranges, e.g., 100 codes of a concentration ranging
from 10 ppm to 1000 ppm in 10 ppm increments. With the advent of
superior concentration and detection techniques (e.g, for smaller
increments), more codes may be constructed.
[0026] Further, the number of unique codes can be increased by
adding additional types and concentrations of the same or different
taggants. A significant increase in the number of possible codes
can be achieved by using more than one taggant in creating the
code. For example, the code can be expanded by adding another
taggant with its own specific concentrations. The number of codes
can be further expanded by adding a third taggant with its own
specific concentrations. Additional taggants could be used to
provide even more codes. This coding system depends on the
concentration increments of each of the taggants.
[0027] The number of codes available in the coding system could
also be increased by varying the location of the taggant(s) within
the material to be detected. For example, the detected material
could be divided into any number of portions (i.e., quadrants) with
certain taggants (or codes) being placed in certain of those
portions, and optionally not in others, to signify additional
information during the XRF analysis.
[0028] When taggants include elements or compounds that may be
found in the target material or in the environment to which the
target material may be exposed, taggant contamination may occur and
possibly render the taggant code difficult to read. For example, if
a taggant comprising titanium oxide is located in carpet as the
targeted material, it is possible that additional amounts of the
taggant(s) could be present in the targeted material as a result of
environmental contamination, an internal chemical reaction, or
other contamination. If this contamination occurs, there will be a
change in the concentration of that taggant in the target material.
Subsequent measurement of this taggant could yield a value
corresponding to an incorrect code.
[0029] In such an instance, it is difficult to determine what
amount of the taggant present in the targeted material is
"contamination" as opposed to taggant present before contamination.
This problem can be solved in target materials for which
contamination might be suspected by using a backup (i.e., duplicate
or otherwise) or secondary system, such as a backup or secondary
taggant(s), backup or secondary code, or backup or secondary
location. See, for example, the description in U.S. Pat. No.
5,760,394, the disclosure of which is incorporated herein by
reference. If desired, more than one such backup or secondary
system can be used. The backup or secondary system can also be used
for other purposes, e.g., to verify the original coding system.
[0030] Any suitable target material can be employed in the present
invention. Suitable target materials include those which
intrinsically contain the desired taggant(s) or in which the
desired taggant(s) can be incorporated. Because XRF detection
measures changes in the inner shell(s) of the taggant, it will not
be significantly modified by chemical reactions that normally occur
in the outer shells. Thus, it is possible to tag chemicals and have
the taggant code be carried in any product manufactured with those
chemicals. Target materials should be comprised of a material in
which XRF detection is easy, e.g., little chance of background
contamination, taggant deterioration, taggant destruction,
contamination, or other deteriorating condition.
[0031] Example of suitable target materials include: paper products
like documents, currency, or tickets; solid products like jewelry,
carpets, plastics, packaging (films, labels, and adhesives),
metals, rubbers (tires), woods, or plastics (credit cards); liquid
products like lubricating fluids, resins, sprays, paints, oils,
inks; hazardous wastes; drugs or pharmaceuticals; gaseous products;
or combinations or hybrids of these materials. Additionally,
suitable target materials--such as paper documents, drugs, or
counterfeit manufactured items--include those that will be
subsequently changed. For example, a target material that is
suspected might be destroyed could be tagged with elements known to
be present in the residue from the destruction. Since the taggant
is not usually changed by the chemical process in destruction, a
connection between the target material and its residue could be
established after destruction. Preferably, the target material of
the present invention is carpeting and carpet products.
[0032] The target materials containing the at least one taggant can
be used for a wide number of applications. For example, tagging
paints would allow any article coated with that paint to be
identified. In another example, tagging paper and ink used in the
paper (or applied to the paper) can be used to establish the
authenticity of documents and currency. In yet another example,
many manufactured items prone to counterfeiting or theft could
benefit from tagging. Tagged threads in clothing could be used to
encode information about the date, time, and place of manufacture.
Tagging the bulk materials used in the manufacture of such items as
compact disks, computer disks, video tapes, audio tapes, electronic
circuits, and other items would be useful in tracing and
prosecuting theft and counterfeiting cases involving these
items.
[0033] In the present invention, the at least one taggant can be
incorporated into the target material in any suitable form.
Suitable forms include those which place that taggant in the target
material with little to no damage (either chemical or physical) to
the target material. See, for example, the description in U.S. Pat.
Nos. 5,208,630, 5,760,394, and 6,030,657, the disclosures of which
are incorporated herein by reference. Other suitable forms include
using materials containing the taggant such as particulates like
microparticles; solvents; coatings and films; adhesives; sprays; or
a hybrid or combination of these methods. In any of these forms,
the at least one taggant can be incorporated by itself or with
another agent.
[0034] The at least one taggant can be incorporated in the target
material using any suitable technique. Many existing tagging
techniques involve the use of microparticles containing the
elements, or compounds or compositions of the elements, comprising
the at least one taggant. Additionally, particles can be
manufactured wherein smaller particles, or compounds or
compositions of the elements, containing the taggant. Such
particles could be made of: magnetic or fluorescent materials to
facilitate collection; refractory materials to enhance particle
survival in an explosion; or chemically inert materials to enhance
particle survival in a chemical reaction. Indeed, such particles
could be made of non-durable, soluble, or reactive materials to
enhance taggant dispersal in a fluid, aerosol, or powder
system.
[0035] When the target material is a liquid article like paints or
inks, or adhesives, or has a liquid component, the at least one
taggant can be incorporated as an element or compound in solution
with the liquid. Thus, the at least one taggant can be incorporated
in elemental or compound form either in solution or suspension in
the target material. The at least one taggant could also be
dissolved or suspended in a solvent used in making the target
material so that when that solvent evaporates, the residue left
behind would contain the at least one taggant.
[0036] The taggant can be inserted into the target material of an
article either during or after the article (or a part thereof) has
been manufactured. The taggant can be manufactured as a component
of the article or as part of a component of the article. During
manufacture, the at least one taggant can also be incorporated into
another material which comprises part of the target material.
Indeed, the at least one taggant could also be an element or
compound of the target material itself. The taggant can be
incorporated into any location (including surfaces) of the article.
Two (and three) dimensional shapes and patterns of the at least one
taggant can be constructed using any desired combination of types
and numbers of taggants.
[0037] The at least one taggant could also be incorporated after
manufacture of the target material of the article. The at least one
taggant could be incorporated into the already formed target
material as a dopant. Additionally, the taggant can be implanted
into the article or deposited as a coating or film on the article.
As a coating or film, the at least one taggant could be physically
or chemically deposited by itself The at least one taggant could
also be incorporated as one ingredient (or contaminant) of another
material (such as a mixture or solution) which forms a coating or
film. In this aspect of the invention, the at least one taggant can
be incorporated as an element or compound in solution (or
suspension) with a liquid which is applied, such as by spraying, to
the article. For example, the at least one taggant could be
dissolved or suspended in a solvent so that when that solvent
evaporates after being applied to the article, the residue left
behind would contain the at least one taggant.
[0038] As apparent from the description above, the present
invention has the ability to easily tag small batches of target
materials with a code unique to that batch. This can be done
manually or in an automated system where each batch (or select
batches) of the target material receives a different code. For
example, 1000 (or 100) compact discs could be manufacture and each
could be tagged with a code of a number from 1 to 1000 (or 1 to
100). Economic and processing considerations, however, might limit
the minimum size of each batch and the number of batches which
could be tagged.
[0039] In one aspect of the invention, the quality of a product (or
a process for manufacturing that product) can be controlled by
detecting or analyzing the at least one taggant in a target
material--or a component thereof--during its manufacture. The
quality of the product (and accompanying manufacturing process) can
be controlled by detecting and analyzing the presence,
concentration, and location of the taggant at any point in the
manufacturing process. For example, the at least one taggant can be
either a component of any raw material used to make the product or
can be added to the raw material to "track" the presence of the raw
material.
[0040] In one aspect of the present invention, the presence,
concentration, and location of those materials comprising a carpet
can be detected and analyzed during its manufacture. Carpets
generally comprise both a yarn and a backing. The yarn may comprise
different types of materials, usually fibers, with differing types
of twists and shapes to change the look of the carpet. The fibers
can be made of plastic materials like nylon, polypropylene,
polyester, and acrylic, or wool, or a combination thereof.
Generally, the carpet fibers are made of one of the above plastic
materials. Carpet and carpet components and their method of
manufacture are known in the art. See, for example, U.S. Pat. No.
6,030,685, the disclosure of which is incorporated herein by
reference.
[0041] The at least one taggant of the present invention,
therefore, could be present in the yarn or backing of the carpet,
or in the materials making up the yarn or backing. For example, the
at least one taggant could be present in the fiber materials as
they are made. In another example, the at least one taggant could
be present in a separate fiber material which could then be
combined with a yarn (not containing any taggant) during the
twisting process. In yet another example, the at least one taggant
could be present in the backing. In another example, a first
extrinsic taggant could easily be incorporated into carpet products
while manufacturing the carpets with a second intrinsic taggant,
which is itself a component of the fiber or backing. In even
another example, the taggant could be part of a coating or film
that is applied to the carpet after its manufacture.
[0042] The at least one taggant could be detected and analyzed at
any point during the manufacturing process of the carpet. Generally
carpets are made by manufacturing the yarn and backing separately.
The yarn is made by making the individual fibers and then twisting
the fibers together into the yarn. The backing is made by foam
processes known in the art. The yarn is then tufted or locked into
the backing in a variety of ways, each affecting the texture and
durability of the carpet.
[0043] Based on the detection and analysis of the taggant, the
manufacturing process for making the carpet could be modified as
desired. For example, where the taggant is a component of the nylon
material used to make the fibers, the detection could provide
important information about the concentration of the nylon. If the
concentration of nylon in the process for making the fibers was too
high, the process could be modified to decrease the concentration
of nylon. A similar analysis and modification could occur when the
taggant has been added to the nylon material for the purpose of
measuring the nylon concentration.
[0044] Indeed, multiple taggants could be used with each taggant
being associated with a different component in the product or
process. For example, a first taggant could be added to the
material for a first set of fibers, a second taggant could be added
to the material for a second set of fibers, a third taggant could
be added to the material for the backing, etc . . . By using
different taggants for different components of the product (or
different parts of the manufacturing process), one is better able
to identify and fix that part of the product (or process) where the
quality is deficient.
[0045] In another example, carpet manufacturers often make fibers
with a specific level of titanium dioxide (TiO.sub.2). The
TiO.sub.2 is often impregnated in the material of the yarn fibers,
e.g., the nylon. TiO.sub.2 makes the carpet appear more like wool
and also exhibits the ability to bind with dyes used in the process
for manufacturing the carpets, thereby enhancing the color of the
carpets. If the carpets are not made with a substantially uniform
TiO.sub.2 concentration throughout the fibers and yarn, there is no
uniform color and consistency. To better control the manufacturing
process, the concentration of TiO.sub.2 in nylon could be measured
in the process of making the fibers. If the detected TiO.sub.2
concentration is not consistent, the process could be modified as
known in the art to achieve the desired consistency.
[0046] In another example, a protective liquid is often applied to
carpet after it has been manufactured. When dried, the protective
liquid forms a coating on the carpet which, among other functions,
protects the fabric of the carpet. It is important for carpet
consumers to have a high quality coating so the protective
functions can be maximized. Thus, it important for carpet
manufacturers to know as much as possible about the quality of the
coating, e.g., to know whether a protective liquid was applied,
which manufacturer's liquid was applied, where the protective
liquid has been applied, and how much (i.e., consistency) of the
protective liquid that has been applied.
[0047] To that end, at least one taggant can be incorporated into
the protective liquid to help control the quality of the process
used in coating the protective liquid on carpet. Using the taggant,
a carpet manufacturer can detect the taggant before, during, or
after applying the protective liquid to assess the quality of the
protective liquid, how it is applied, and the quality of the
coating. For example, XRF detection of an unknown carpet could
determine, based on its composition, whether a protective coating
is present. 20 Additionally, any particular manufacturer--knowing
that specific carpets are coated with a protective liquid
containing a given taggant(s--could determine whether his
particular protective liquid has been used.
[0048] Further, XRF detection of the concentration of a known
taggant in a known carpet at several locations would allow the
manufacturer to determine the consistency of the application. The
analysis would show how uniformly the protective liquid was applied
and the amount of liquid that has dried into a coating at any given
location. Based on the information obtained, the manufacturer could
then change the parameters of the coating process (or drying
process) as known in the art to obtain a more uniform protective
coating.
[0049] As an example of the above concepts, a taggant could be
added to a protective liquid by injecting a solid (i.e.,
microparticle) or liquid (e.g., solvent) containing the at least
one taggant into the bulk material of protective liquid before that
liquid is coated on a carpet. Alternatively, a taggant solution
could be prepared by mixing a taggant with water and then adding
the taggant solution to the protective liquid to create a tagged
protective liquid. The tagged protective liquid could then be
coated onto the carpet sample by soaking for a specified period of
time. The carpet could then be dried under specified conditions
until the liquid portion of the tagged protective liquid
evaporates, leaving the taggant as a component of a film on the yam
and backing of the carpet. Numerous locations along the length and
width of the carpet sample could be selected for XRF detection and
analysis. The difference in taggant concentration over the
locations could be measured to find the consistency of the
protective coating. If the desired consistency was not obtained, a
different soaking method (or different method of application such
as spraying) could be used, a different drying process could be
employed, and/or another process parameter could be changed.
[0050] The ability to monitor and assess the quality of a product
and its accompanying manufacturing process using XRF detection of
taggants becomes even more important with certain materials. Some
materials are troublesome because they are "low z" materials, e.g.,
they have a low atomic number, which are difficult to detect via
XRF. By incorporating a taggant which is more easily detected--by
having a high atomic number--with such low z materials, the quality
of a product containing low z materials (and the accompanying
manufacturing process) become easier to control and monitor.
[0051] After the at least one taggant is extrinsically or
intrinsically present in the target material(s), the taggant(s) is
detected to identify or verify the target material using XRF
analysis as illustrated in FIG. 1. Primary x-rays 40 are used to
excite a sample of the target material 46, and the secondary x-rays
44 that are emitted by the sample are detected and analyzed.
[0052] As shown in FIG. 3, the x-rays which are detected have
various energies, e.g., there is a broad band of scattered x-rays
with energies less than and greater than those of the exciting
atom. FIG. 3 illustrates this spectrum for paper as the target
material. Within this broad band, there are peaks due to the
excitation of the taggant(s) in the sample. The ratio of the
intensity of the radiation in any peak to the intensity of the
background at the same energy (known as the peak-to-background
ratio) is a measure of the concentration of the element which has
characteristic X-rays at the energy of that peak, e.g., the
taggant.
[0053] In one aspect of the detection method of the present
invention, at least one target material believing to contain known
concentrations of the taggant(s) of interest is selected. The XRF
analysis is performed on that target material (or a sample thereof)
using a detection device or apparatus containing an x-ray radiation
source ("source"), x-ray radiation detector ("detector"), support
means, analyzer means, and calibration means.
[0054] One aspect of the detection device of the present invention
is illustrated in FIG. 4a. In this Figure, the detection apparatus
25 has an ordinary x-ray fluorescence spectrometer capable of
detecting elements present in a coating, package or material.
X-rays 29 from a source (e.g., either x-ray tube or radioactive
isotope) 20 impinge on a sample 11 which absorbs the radiation and
emits x-rays 31 to an x-ray detector 21 and analyzer 23 capable of
energy or wavelength discrimination. This is accomplished by using
a commercially available x-ray spectrometer such as an Edax DX-95
or a MAP-4 portable analyzer, commercially available from Edax
Inc., Mahwah, N.J. Part of analyzer 23 includes a computerized
system 27.
[0055] Another aspect of the detection apparatus of the present
invention is illustrated in FIG. 4b. In this Figure, the detection
apparatus 25 has an instrument housing 15 which contains the
various components. Gamma rays or x-rays 30 from a source (e.g.,
either x-ray tube or radioactive isotope) 20 are optionally focused
by aperture 10 to impinge on a sample 11. Sample 11 contains the at
least one taggant which absorbs the radiation and emits x-rays 31
to an x-ray detector 21. Optionally, analyzing means can be
incorporated within housing 15.
[0056] The present invention, however, is not limited to the
detection apparatus depicted in FIGS. 4a and 4b. Any suitable
source, or plurality of sources, known in the art can be used as
the source in the detection device of the present. See, for
example, U.S. Pat. Nos. 4,862,143, 4,045,676, and 6,005,915, the
disclosures of which are incorporated herein by reference. During
the XRF detection process, the source bombards the taggant with a
high energy beam. The beam may be an electron beam or
electromagnetic radiation such as X-rays or gamma rays. The source,
therefore, may be any material which emits such high energy beams.
Typically, these have been x-ray emitting devices such as x-ray
tubes or radioactive sources.
[0057] To target, the beam can be focused and directed properly by
any suitable means such as an orifice or an aperture. The
configuration (size, length, diameter . . . ) of the beam should be
controlled, as known in the art, to obtain the desired XRF
detection. The power (or energy level) of the source should also be
controlled, as known in the art, to obtain the desired XRF
detection.
[0058] The source(s) can be shielded and emit radiation in a space
limited by the shape of the shield. Thus, the presence,
configuration, and the material used for shielding the source
should be controlled for consistent XRF detection. Any suitable
material and configuration for that shield known in the art can be
employed in the present invention. Preferably, any high-density
materials used as the material for the shield, e.g, tungsten or
brass.
[0059] Any suitable detector, or plurality of detectors, known in
the art can be used as the detector in the detection device of the
present invention. See, for example, U.S. Pat. Nos. 4,862,143,
4,045,676, and 6,005,915, the disclosures of which are incorporated
herein by reference. Any type of material capable of detecting the
photons omitted by the taggant may be used. Silicon and CZT
(cadmium-zinc-telluride) detectors have been conventionally used,
but others such as proportional counters, germanium detectors, or
mercuric iodide crystals can be used.
[0060] Several aspects of the detector should be controlled to
obtain the desired XRF detection. First, the geometry between the
detector and the target material should be controlled. The XRF
detection also depend on the presence, configuration, and
material--such as tungsten and beryllium--used as a window to allow
x-rays photons to strike the detector. The age of the detector,
voltage, humidity, variations in exposure, and temperature can also
impact the XRF detection and, therefore, these conditions should be
controlled.
[0061] The analyzer means sorts the radiation detected by the
detector into one or more energy bands and measures its intensity.
Thus, any analyzer means performing this function could be used in
the present invention. The analyzer means can be a multi-channel
analyzer for measurements of the detected radiation in the
characteristic band and any other bands necessary to compute the
value of the characteristic radiation as distinct from the
scattered or background radiation. See, for example, U.S. Pat. Nos.
4,862,143, 4,045,676, and 6,005,915, the disclosures of which are
incorporated herein by reference.
[0062] The XRF also depends on the resolution of the x-rays.
Background and other noise must be filtered from the x-rays for
proper measurement, e.g., the signals must be separated into the
proper number of channels and excess noise removed. The resolution
can be improved by cooling the detector using a thermoelectric
cooler--such as a nitrogen or a peltier cooler--and/or by
filtering. Another way to improve this resolution is to use
pre-amplifiers.
[0063] The support means supports the source and detector in
predetermined positions relatively to a sample of the target
material to be irradiated. Thus, any support means performing this
function could be used in the present invention. In one example,
the support means comprises two housings, where the source and
detector are mounted in a first housing which is connected by a
flexible cable to a second housing in which the analyzer means is
positioned as illustrated in FIG. 4a. If desired, the first housing
may then be adapted to be hand-held. In another example, the source
and detector as well as the other components of the detection
device are mounted in a single housing as illustrated in FIG.
4b.
[0064] The calibration means are used to calibrate the detection
apparatus, thus insuring accuracy of the XRF analysis. In this
calibration, the various parameters which could be modified and
effect the measurement are isolated and calibrated. For example,
the geometrical conditions or arrangements can be isolated and
calibrated. In another example, the material matrix are isolated
and calibrated. Preferably, internal (in situ) calibration during
detection is employed as the calibration means in the present
invention. Components, such as tungsten shielding, are already
present to internally calibrate during the XRF analysis. Other
methods, such as fluorescence peak or Compton backscattering, could
be used for internal calibration in the present invention.
[0065] Analyzer means, which includes a computerized system 27, is
coupled to, receives, and processes the output signals produced by
detector 21. The energy range of interest, which includes the
energy levels of the secondary x-ray photons 44 emitted by the
taggant(s), is divided into several energy subranges. Computerized
system 27 maintains counts of the number of X-ray photons detected
within each subrange using specific software programs, such as
those to analyze the detection and x-ray interaction and to analyze
backscatter data. After the desired exposure time, computerized
system 27 with display menus stops receiving and processing output
signals and produces a graph of the counts associated with each
subrange.
[0066] FIG. 5 is a representative graph of the counts associated
with each subrange. This graph is essentially a histogram
representing the frequency distribution of the energy levels E1,
E2, and E3 of the detected x-ray photons. Peaks in the frequency
distribution (i.e., relatively high numbers of counts) occur at
energy levels of scattered primary x-ray photons as well as the
secondary x-ray photons from the taggant(s). A primary x-ray photon
incident upon a target material may be absorbed or scattered. The
desired secondary x-ray photons are emitted only when the primary
x-ray photons are absorbed. The scattered primary x-ray photons
which reach the detector of the system create an unwanted
background intensity level. Accordingly, the sensitivity of XRF
analysis is dependent on the background intensity level, and the
sensitivity of XRF detection may be improved by reducing the amount
of scattered primary x-ray photons reaching the detector. The peak
occurring at energy levels of scattered primary x-ray photons is
basically ignored, while the other peaks--those occurring at E1,
E2, and E3--are used to identify the at least one taggant present
in the target material.
[0067] Besides the parameters described above, at least two other
parameters must be controlled during the process of XRF detection.
First, the media (such as air) through which the gamma rays (and
x-rays) must travel also impacts the XRF. Therefore, the different
types of media must be considered when performing the XRF analysis.
Second, the methods used to interpret and analyze the x-rays
depend, in large part, on the algorithms and software used. Thus,
methods must be adopted to employ software and algorithms that will
consistently perform the XRF detection.
[0068] These two parameters, plus those described above, must be
carefully accounted for and controlled to obtain accurate
measurements. In one aspect of the intention, these parameters
could be varied and controlled to another provide a distinct code.
For example, using a specific source and a specific detector with a
specific measuring geometry and a specific algorithm could provide
one distinct code. Changing the source, detector, geometry, or
algorithm could provide a whole new set of distinct codes.
[0069] FIG. 6 illustrates a preferred apparatus and detection
method according to the present invention. In this Figure,
detection apparatus 25 is capable of detecting at least one taggant
present in target material 10, such as a sample of carpet.
Detection apparatus 25 is a portable device which can be small
enough to be hand-held. Detection apparatus 25 contains all the
components discussed above (i.e., source, detector, analyzer means,
and calibration means) in a single housing, thus allowing the
portability and smaller size.
[0070] The present invention is not limited to any specific XRF
analysis. Any type of XRF, such as total reflection x-ray
fluorescence (TXRF), can be employed in the present invention.
[0071] In one aspect of the invention, the apparatus and method
used identify an article once it has been tagged. The ability to
invisibly tag an article and read the tag, especially through a non
line-of-sight method, would provide an invaluable asset in any
industry that authenticates, verifies, tracks, labels, or
distributes goods of any kind. Indeed, having an invisible
taggant(s) could further prevent copying and counterfeiting of
goods. In another aspect of the invention, the apparatus and method
of the present invention could be used for these same purposes, but
for those products that have the desired taggant already located
therein. Thus, the present inventions could analyze liquid flows
for contaminant particles or pinpoint via 3-D analysis the exact
location of a contaminant(s) in an article.
[0072] The following non-limiting example illustrates the present
invention.
EXAMPLE
[0073] Several carpet samples were obtained and analyzed via XRF.
The samples showed high amounts of strontium in the carpet backing.
Strontium exhibits K.sub. and K.sub. peaks in the XRF spectrum.
[0074] 1 liter of a commercially-available protective liquid was
purchased. Varying amounts of zirconium taggant (and, if necessary,
distilled water) were added to the protective liquid to obtain
taggant concentrations of 0, 2, 4, 6, 8, and 10 ppm. The tagged
protective liquid was then coated onto the carpet samples by
soaking. The carpet samples were wrung out and dried until the
liquid portion of the tagged protective liquid evaporated, leaving
the zirconium as a component of a film on the carpet.
[0075] The presence of the zirconium taggant was then detected with
XRF. Since the concentrations of zirconium were low, the large
strontium K.sub. peak of the strontium effectively encompassed the
peak provided by the zirconium. See FIG. 7.
[0076] To substantially eliminate the substantial strontium peak, a
silver plate was constructed to collimate the gamma rays so that
they illuminated only the first few centimeters of the carpet
fiber. This modification reduced the amount of strontium
fluorescence so the differences in zirconium between carpet samples
could be detected and calibrated for. See FIG. 8.
[0077] A portable, hand-held detection apparatus similar to that
illustrated in FIG. 6 was then calibrated to detect the presence of
the different zirconium amounts using XRF. The detection apparatus
contained several components. A trigger actuated tungsten shutter
block containing a Cadmium 109 gamma ray point source, a silicon
pin X-ray detector and silver collimator were located within the
front of the instrument. Circuit boards, necessary for acquiring
and processing the data from the detector were located within the
rest of the housing. A keypad on the top of the instrument allowed
the user to turn the electronics of the instrument on and off,
while a key operated lock on the side of the instrument kept the
user from inadvertently opening the shutter block, exposing the
radioactive source. The instrument had a display to inform the user
whether the carpet sample was treated with the tagged protective
liquid and the concentration of the taggant.
[0078] The carpet samples containing the different concentrations
of the zirconium taggant were analyzed with this detection
apparatus. The data collected from these assays were analyzed to
obtain a correlation between the thickness of the protective film
and 20 zirconium content. Using this correlation, the
thickness--and therefore quality--of the protective film for a
carpet sample produced using a similar process could then be
estimated based on its detected zirconium concentration.
[0079] Having described the preferred aspects of the present
invention, it is understood that the invention defined by the
appended claims is not to be limited by particular details set
forth in the above description, as many apparent variations thereof
are possible without departing from the spirit or scope
thereof.
* * * * *