U.S. patent application number 13/627392 was filed with the patent office on 2013-08-08 for metal authenticity testing of an object using radiation.
This patent application is currently assigned to THERMO NITON ANALYZERS LLC. The applicant listed for this patent is THERMO NITON ANALYZERS LLC. Invention is credited to Michael E. Dugas, Stanislaw Piorek, Stephen I. Shefsky.
Application Number | 20130202084 13/627392 |
Document ID | / |
Family ID | 47740753 |
Filed Date | 2013-08-08 |
United States Patent
Application |
20130202084 |
Kind Code |
A1 |
Piorek; Stanislaw ; et
al. |
August 8, 2013 |
METAL AUTHENTICITY TESTING OF AN OBJECT USING RADIATION
Abstract
Techniques disclosed herein include systems and methods for
identifying counterfeit gold jewelry and other counterfeit gold
items. Techniques include determining--using a non-destructive
mechanism--whether an item of interest (such as an article
represented as true gold) is solid gold or a gold-plated object.
Techniques include using an X-ray fluorescence (XRF) analyzer to
differentiate true gold from gold plating. The XRF analyzer can
distinguish between gold plating and bulk gold material by
comparing a ratio of L-alpha and L-beta x-ray lines of gold. The
analyzer measures a ratio of intensities of characteristic L-lines
of gold using X-ray fluorescence (XRF) spectroscopy. When
implemented using an XRF analyzer, the system nondestructively
determines whether a test object is made of solid gold/gold alloy
or has gold plating only.
Inventors: |
Piorek; Stanislaw;
(Hillsborough, NJ) ; Shefsky; Stephen I.;
(Brooklyn, NY) ; Dugas; Michael E.; (Londonderry,
NH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THERMO NITON ANALYZERS LLC; |
Billerica |
MA |
US |
|
|
Assignee: |
THERMO NITON ANALYZERS LLC
Billerica
MA
|
Family ID: |
47740753 |
Appl. No.: |
13/627392 |
Filed: |
September 26, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13365713 |
Feb 3, 2012 |
|
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13627392 |
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Current U.S.
Class: |
378/45 |
Current CPC
Class: |
G01N 2223/633 20130101;
G01N 23/223 20130101; G01N 2223/076 20130101; G01B 15/02
20130101 |
Class at
Publication: |
378/45 |
International
Class: |
G01N 23/223 20060101
G01N023/223 |
Claims
1. A method comprising: directing an x-ray excitation beam onto at
least a portion of an item of interest, the x-ray excitation beam
causing the item of interest to fluorescently emit x-rays at
various energies; measuring an intensity of a first energy that
corresponds to an alpha energy emission line of gold, the first
energy identified from x-rays fluorescently emitted from the item
of interest; measuring an intensity of a second energy that
corresponds to a beta energy emission line of gold, the second
energy identified from x-rays fluorescently emitted from the item
of interest; calculating a ratio of measured intensities between
the intensity of the first energy and the intensity of the second
energy; and in response to identifying that the calculated ratio is
beyond a predetermined value, producing an indication that the item
of interest is gold-plated.
2. The method of claim 1, wherein the predetermined value is a gold
lines intensity ratio representing a gold thickness of more than
about 15 microns, wherein the calculated ratio is beyond the
predetermined value indicating a thickness of gold less than about
15 microns.
3. The method of claim 1, wherein the predetermined value is a
ratio value of approximately 0.84, and the calculated ratio is
greater than 0.84.
4. The method of claim 3, wherein the predetermined value is a
first predetermined value, the method further comprising: in
response to identifying that the calculated ratio is less than a
second predetermined value, indicating that the item of interest is
gold-plated.
5. The method of claim 4, wherein the second predetermined value is
a ratio value of approximately 0.60.
6. The method of claim 1, further comprising: analyzing a spectrum
of x-rays fluorescently emitted from the item of interest to
identify a percentage composition of gold in the item of interest
with respect to other elements in the item of interest; and in
response to identifying that the concentration of gold in the item
of interest is less than about 33 percent, confirming that the item
of interest is gold-plated.
7. The method of claim 6, further comprising: identifying a
percentage composition of nickel from the item of interest relative
to other elements in the item of interest by analyzing the spectrum
of x-rays fluorescently emitted from the item of interest; and in
response to identifying that the concentration of nickel is greater
than about 10 percent, confirming that the item of interest is
gold-plated.
8. The method of claim 6, further comprising: wherein identifying a
percentage composition of gold includes executing bulk analysis of
elemental composition of the item of interest using either an
energy dispersive XRF (X-Ray Fluorescence) analyzer or a wavelength
dispersive XRF analyzer.
9. The method of claim 5, further comprising: analyzing a spectrum
of x-rays fluorescently emitted from the item of interest to
identify a percentage composition of silver from the item of
interest relative to other elements in the item of interest; in
response to identifying that the concentration of silver is less
than about 20 percent, indicating that the item of interest is
gold-plated brass; and in response to identifying that the
concentration of silver is greater than about 20 percent,
indicating that the item of interest is either gold-plated brass or
gold-plated silver.
10. The method of claim 1, wherein the item of interest is
jewelry.
11. (canceled)
12. The method of claim 1, further comprising: in addition to
indicating that the item of interest is gold-plated, indicating an
approximate thickness of gold plating on the item of interest.
13. An x-ray fluorescence (XRF) analyzer comprising: an x-ray
source that generates an x-ray excitation beam to be directed onto
at least a portion of an item of interest; an x-ray detector
positioned to receive x-rays emitted from the item of interest, the
emitted x-rays including fluorescently emitted x-rays at a first
energy that corresponds to an alpha energy emission line of gold,
the emitted x-rays also including fluorescently emitted x-rays at a
second energy that corresponds to a beta energy emission line
emission of gold, the x-ray detector producing signals indicating
intensities of the fluorescently emitted x-rays; a signal processor
coupled to the x-ray detector, the signal processor calculating a
ratio of measured intensities between an intensity of the first
energy and an intensity of the second energy; and a display
indicating that the item of interest is gold-plated in response to
the signal processor identifying that the calculated ratio is
beyond a predetermined value.
14. The XRF analyzer of claim 13, wherein the predetermined value
is a gold lines intensity ratio representing a gold thickness of
more than about 15 microns; and wherein the calculated ratio is
greater than the predetermined value, which indicates a thickness
of gold less than about 15 microns.
15. The XRF analyzer of claim 13, wherein the predetermined value
is a threshold ratio value of approximately 0.84, and the
calculated ratio is greater than approximately 0.84.
16. The XRF analyzer of claim 15, wherein the display further
indicates that the item of interest is gold-plated in response to
the signal processor identifying that the calculated ratio is less
than a second predetermined value, the second predetermined value
being a ratio value of approximately 0.60.
17. The XRF analyzer of claim 13, wherein the signal processor is
further configured to: identify a percentage composition of gold
from the item of interest relative to other elements in the item of
interest by analyzing a spectrum of x-rays fluorescently emitted
from the item of interest; in response to identifying that the
concentration of gold is less than about 33 percent, indicate that
the item of interest is gold-plated; identify a percentage
composition of nickel from the item of interest relative to other
elements in the item of interest by analyzing the spectrum of
x-rays fluorescently emitted from the item of interest; and in
response to identifying that the concentration of nickel is greater
than about 10 percent, indicate that the item of interest is
gold-plated.
18. The XRF analyzer of claim 13, wherein the signal processor is
further configured to: identify a percentage composition of silver
from the item of interest relative to other elements in the item of
interest by analyzing a spectrum of x-rays fluorescently emitted
from the item of interest; in response to identifying that the
concentration of silver is less than about 20 percent, indicate
that the item of interest is gold-plated brass; and in response to
identifying that the concentration of silver is greater than about
20 percent, indicate that the item of interest is either
gold-plated brass or gold-plated silver.
19. A computer-implemented method for identifying gold plating on
objects from x-ray fluorescence (XRF), the computer-implemented
method comprising: receiving data corresponding to x-rays that have
been fluorescently emitted at various energies from an item of
interest; receiving an intensity of a first energy that corresponds
to an alpha energy emission line of gold, the first energy
identified from x-rays fluorescently emitted from the item of
interest; receiving an intensity of a second energy that
corresponds to a beta energy emission line of gold, the second
energy identified from x-rays fluorescently emitted from the item
of interest; calculating a ratio of measured intensities between
the intensity of the first energy and the intensity of the second
energy; and in response to identifying that the calculated ratio is
beyond a predetermined value, indicating that the item of interest
is gold-plated.
20. The computer-implemented method of claim 19, wherein the
predetermined value is a gold lines intensity ratio representing a
gold thickness of more than about 15 microns, wherein the
calculated ratio being beyond the predetermined value indicates a
thickness of gold less than about 15 microns.
21. The XRF analyzer of claim 15, wherein the XRF analyzer is
selected from the group consisting of energy dispersive XRF
analyzer and wavelength dispersive XRF analyzer.
22. The method of claim 1, wherein the first energy corresponds to
an alpha energy emission of gold around 9.71 keV; and wherein the
second energy corresponds to a beta energy emission of gold around
11.45 keV; and wherein the predetermined value is a gold lines
intensity ratio representing a saturation plateau of gold at which
the gold lines intensity ratio is substantially constant regardless
of thickness.
23. The method of claim 1, wherein calculating the ratio includes:
dividing the measured intensity of the first energy by the measured
intensity of the second energy.
24. The method of claim 23, wherein the predetermined value is a
gold lines intensity ratio representing a gold thickness of more
than about 15 microns, wherein the calculated ratio is greater than
the predetermined value indicating a thickness of gold less than
about 15 microns.
25. The method of claim 24, wherein the predetermined value is a
ratio value of approximately 0.84, and the calculated ratio is
greater than 0.84.
26. The method of claim 25, wherein the first energy corresponds to
an alpha energy emission of gold around 9.71 keV; and wherein the
second energy corresponds to a beta energy emission of gold around
11.45 keV.
27. The method of claim 1, wherein the predetermined value
represents a gold lines intensity ratio value disposed between a
first range of gold lines intensity ratios in which the sample gold
lines intensity ratio for gold substantially varies depending on
gold thickness and a second range of intensity ratios in which the
gold lines intensity ratio is substantially constant regardless of
sample gold thickness.
28. A method comprising: directing an x-ray excitation beam onto at
least a portion of an item of interest, the x-ray excitation beam
causing the item of interest to fluorescently emit x-rays at
various energies; measuring an intensity of a first energy that
corresponds to an alpha energy emission line of gold, the first
energy identified from x-rays fluorescently emitted from the item
of interest; measuring an intensity of a second energy that
corresponds to a beta energy emission line of gold, the second
energy identified from x-rays fluorescently emitted from the item
of interest; calculating a ratio of measured intensities between
the intensity of the first energy and the intensity of the second
energy; and in response to identifying that the calculated ratio
falls outside of a ratio range, producing an indication that the
item of interest is gold-plated.
29. The method as in claim 28, wherein calculating the ratio
includes dividing the intensity of the first energy in the alpha
energy emission line of gold by the intensity of the second energy
in the beta energy emission line of gold.
30. An apparatus comprising: an x-ray source, the x-ray source
exposing an item of interest to x-ray excitation radiation; an
x-ray detector positioned to receive x-rays fluorescently emitted
from the item of interest; and a signal processor coupled to the
x-ray detector, the signal processor classifying the item of
interest based at least in part on a calculated ratio compared to a
predetermined value, the calculated ratio derived from an intensity
of fluorescently emitted energy at a first energy level from the
item of interest with respect to an intensity of fluorescently
emitted energy at a second energy level from the item of
interest.
31. The apparatus as in claim 30, wherein the predetermined value
is a gold lines intensity ratio representing a saturation plateau
of gold at which the gold lines intensity ratio is substantially
constant over a range of gold thickness.
32. The apparatus as in claim 30, wherein the signal processor
classifies the item of interest as being a substrate coated with a
metal material in response to detecting that the calculated ratio
falls outside of a range, one endpoint of the range define by the
predetermined value.
33. The apparatus as in claim 31, wherein the gold lines intensity
ratio represents a gold thickness of around 15 microns, the
calculated ratio greater than the predetermined value, indicating a
thickness of gold on the item of interest as being less than around
15 microns.
34. The apparatus as in claim 33, wherein the calculated ratio
equals the intensity of fluorescently emitted energy at the first
energy level divided by the intensity of fluorescently emitted
energy at the second energy level; and wherein the first energy
level corresponds to an alpha energy emission of gold around 9.71
keV; and wherein the second energy level corresponds to a beta
energy emission of gold around 11.45 keV.
Description
RELATED APPLICATIONS
[0001] This Patent Application is a Continuation of and claims
priority to U.S. patent application Ser. No. 13/365,713 filed on
Feb. 3, 2012, entitled, "SYSTEM AND METHOD FOR IDENTIFICATION OF
COUNTERFEIT GOLD JEWELRY USING XRF", the entire teachings of which
are incorporated herein by this reference.
BACKGROUND
[0002] The present invention relates to methods for determining the
concentration of a specified elemental substance employing x-ray
fluorescence techniques, and, more particularly, to methods for
determining elemental concentrations of precious metals.
[0003] Ornamental gold jewelry is typically made from just a
handful of gold alloys. Such gold alloys include gold as a major
component, which is most often combined with other metals such as
copper, zinc, silver and nickel. Gold jewelry that is composed of
either solid gold or a solid gold alloy, is relatively expensive
compared to other types of jewelry. Less expensive jewelry is often
produced of a common alloy such as brass (or sometimes silver).
This common alloy is then plated or clad with layer of gold or a
layer of gold alloy. To comply with laws governing gold commerce,
such jewelry must be properly marked to indicate the type and
quality of the gold layer. For example, such labels can include
"gold plated" or "gold electroplated" for plated objects, as well
as "gold filled" for objects made of gold-clad brass or silver. In
a specific example, gold-plated sterling silver is a recognized
jewelry material as long as a given gold-plated sterling silver
item is recognized as such.
[0004] Gold prices, especially recently, have been rising at an
accelerated rate. The rise in gold prices is accompanied by a high
demand for gold. Due to the high demand for gold and its
accompanying high price, the jewelry market is flooded with brass
and copper articles plated with thin layers of gold purporting to
be gold objects, but instead are fakes. While such gold-plated
articles are legitimate and permissible under trade laws when
accurately identified as a plated object, significant amounts of
gold-plated articles are being passed off as, or are being
identified as, being made of solid gold, or a solid gold alloy.
Gold-plated items can be offered for sale, for example, to a gold
reseller, such as in the case of a consumer selling personal
jewelry items for cash. During a purchase of a gold item (such as
gold jewelry), the purchaser typically evaluates the gold to
determine its worth. This is usually a very fast process that does
not permit detailed analysis. It is common for gold purchasers to
purchase items represented as solid gold or as a solid gold alloy,
when in reality the purchased items are instead simply gold-plated
metal. Purchasing gold-plated items when represented as solid gold
or solid gold alloy results in a significant loss from a purchase
transaction. Accordingly, there is a need for a quick and accurate
method of detecting counterfeit gold.
SUMMARY
[0005] Conventional techniques for verifying bulk gold are
partially destructive and/or time consuming in nature. Such
conventional techniques can include acid tests and scratch tests.
For example, with a scratch test a file is used to scratch the
surface of a gold item. After the gold item is scratched, the gold
item can then be visually inspected to determine if there is a
substrate made of a different material or different alloy. Such
scratch tests are a destructive technique. In cases where a
scratched gold item turns out to be solid gold, then the value of
the gold item would be reduced and/or need subsequent restoration.
An acid test is similarly destructive because a sample from a gold
item needs to be taken to determine a karat value and/or substrate
composition. In many gold-buying situations, such testing is either
unavailable, too time-consuming to keep up with a purchase
transaction rate, or undesirable due to its destructive nature.
After purchases are completed, purchased gold items can be tested
(possibly at a location other than the purchase site) to verify
that the purchases are indeed gold or gold alloy. Unfortunately,
without testing prior to purchase, it is possible to purchase gold
items as true gold when the gold items are in reality gold-plated.
This means that purchasers might pay 10, 100 or 1000 times more
then the gold items are actually worth.
[0006] Techniques disclosed herein include systems and methods for
identifying counterfeit gold jewelry. Techniques include
determining--using a non-destructive mechanism--whether an item of
interest (such as an article represented as true gold) is solid
gold or gold-plated, among other things. Techniques include using
x-ray analyzers to differentiate true gold from gold plating. An
analyzer uses x-ray fluorescence by reading a spectrum of x-rays
returning from a bulk material. The analyzer can detect metals in
the substrate material (below any gold-plating). These detected
metals can include lead, copper, zinc, silver, or other substrate
materials. The analyzer can distinguish between gold plating and
bulk gold material by comparing a ratio of L-alpha and L-beta x-ray
lines of gold from gold plating to that of the bulk gold
material.
[0007] One embodiment includes an X-ray fluorescence (XRF) analyzer
that executes a counterfeit gold detection process or system. An
XRF analyzer directs an x-ray excitation beam onto at least a
portion of an item of interest, such as a gold item represented as
solid gold. The x-ray excitation beam is directed such that the
x-ray excitation beam causes the item of interest to fluorescently
emit x-rays at various energies characteristic for the metallic
elements contained in the item of interest. The XRF analyzer then
measures an intensity of a first energy (L-alpha) that corresponds
to gold (has characteristic atomic signature of gold). This first
energy is identified from x-rays fluorescently emitted from the
item of interest. The XRF analyzer also measures an intensity of a
second energy (L-beta) that corresponds to gold. This second energy
is identified from x-rays fluorescently emitted from the item of
interest. The XRF analyzer can then calculate a ratio of measured
intensities between the intensity of the first energy and the
intensity of the second energy. In response to identifying that the
calculated ratio is beyond a predetermined value, the XRF analyzer
indicates that the item of interest is gold-plated. Such an
indication can mean counterfeit gold when the item of interest is
represented as solid gold instead of as gold-plated. The XRF
analyzer can be embodied as a process, as a device (such as a
portable testing device), or otherwise.
[0008] Other embodiments herein include software programs to
perform the steps and operations summarized above and disclosed in
detail below. One such embodiment comprises a computer program
product that has a computer-storage medium (e.g., a non-transitory,
tangible, computer-readable media, disparately located or commonly
located storage media, computer storage media or medium, etc.)
including computer program logic encoded thereon that, when
performed in a computerized device having a processor and
corresponding memory, programs the processor to perform (or causes
the processor to perform) the operations disclosed herein. Such
arrangements are typically provided as software, firmware,
microcode, code data (e.g., data structures), etc., arranged or
encoded on a computer readable storage medium such as an optical
medium (e.g., CD-ROM), floppy disk, hard disk, one or more ROM or
RAM or PROM chips, an Application Specific Integrated Circuit
(ASIC), a field-programmable gate array (FPGA), and so on. The
software or firmware or other such configurations can be installed
onto a computerized device to cause the computerized device to
perform the techniques explained herein.
[0009] Accordingly, one particular embodiment of the present
disclosure is directed to a computer program product that includes
one or more non-transitory computer storage media having
instructions stored thereon for supporting operations such as:
directing an x-ray excitation beam onto at least a portion of an
item of interest such that the x-ray excitation beam causes the
item of interest to fluorescently emit x-rays at various energies;
measuring an intensity of a first energy that corresponds to gold,
the first energy identified from x-rays fluorescently emitted from
the item of interest; measuring an intensity of a second energy
that corresponds to gold, the second energy identified from x-rays
fluorescently emitted from the item of interest; calculating a
ratio of measured intensities between the intensity of the first
energy and the intensity of the second energy; and in response to
identifying that the calculated ratio is beyond a predetermined
value, indicating that the item of interest is gold-plated. The
instructions, and method as described herein, when carried out by a
processor of a respective computer device, cause the processor to
perform the methods disclosed herein.
[0010] Other embodiments of the present disclosure include software
programs to perform any of the method embodiment steps and
operations summarized above and disclosed in detail below.
[0011] Of course, the order of discussion of the different steps as
described herein has been presented for clarity sake. In general,
these steps can be performed in any suitable order.
[0012] Also, it is to be understood that each of the systems,
methods, apparatuses, etc. herein can be embodied strictly as a
software program, as a hybrid of software and hardware, or as
hardware alone such as within a processor, or within an operating
system or within a software application, or via a non-software
application such as person performing all or part of the
operations.
[0013] As discussed above, techniques herein are well suited for
use in software applications supporting identification of gold
plating. It should be noted, however, that embodiments herein are
not limited to use in such applications and that the techniques
discussed herein are well suited for other applications as
well.
[0014] Additionally, although each of the different features,
techniques, configurations, etc. herein may be discussed in
different places of this disclosure, it is intended that each of
the concepts can be executed independently of each other or in
combination with each other. Accordingly, the present invention can
be embodied and viewed in many different ways.
[0015] Note that this summary section herein does not specify every
embodiment and/or incrementally novel aspect of the present
disclosure or claimed invention. Instead, this summary only
provides a preliminary discussion of different embodiments and
corresponding points of novelty over conventional techniques. For
additional details and/or possible perspectives of the invention
and embodiments, the reader is directed to the Detailed Description
section and corresponding figures of the present disclosure as
further discussed below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The foregoing and other objects, features, and advantages of
the invention will be apparent from the following more particular
description of preferred embodiments herein as illustrated in the
accompanying drawings in which like reference characters refer to
the same parts throughout the different views. The drawings are not
necessarily to scale, with emphasis instead being placed upon
illustrating the embodiments, principles and concepts.
[0017] FIG. 1 is a schematic view of an instrument for detecting
gold plating according to embodiments herein.
[0018] FIG. 2 is a plot diagram showing a ratio of gold x-ray lines
as a function of plating thickness.
[0019] FIG. 3 is a flowchart illustrating an example of a process
supporting gold plating detection according to embodiments
herein.
[0020] FIG. 4 is an example block diagram of a XRF analyzer
operating in a computer/network environment according to
embodiments
DETAILED DESCRIPTION
[0021] Techniques disclosed herein include systems and methods for
identifying counterfeit gold jewelry and other counterfeit gold
items. Techniques include determining--using a non-destructive
mechanism--whether an item of interest (such as an article
represented as true gold) is solid gold or gold-plated, among other
things.
[0022] Techniques include using an x-ray analyzer to differentiate
true gold from gold plating. The analyzer uses x-ray fluorescence
by reading a spectrum of x-rays returning from a bulk material. The
analyzer can detect metals in the substrate material (below any
gold-plating). These detected metals can include lead, copper,
zinc, silver or other substrate materials. The analyzer can
distinguish between gold plating and bulk gold material by
comparing a ratio of L-alpha and L-beta x-ray lines of gold. The
analyzer measures a ratio of intensities of characteristic L-lines
of gold using X-ray fluorescence (XRF) spectroscopy. When
implemented using an XRF analyzer, the system nondestructively
measures the ratio of the L-lines of gold excited in a test object
and determines whether the test object is made of solid gold/gold
alloy or has gold plating only.
[0023] X-ray fluorescence involves directing x-rays from an
external source such as x-ray tube at a material or item of
interest. These external x-rays interact with atoms of the material
or item of interest. Some of the x-rays can knock out the electrons
from a lower energy shell of the atom, which results in electrons
from a higher shell filling the gap. This process causes a release
of energy, by the atom, in the form of an x-ray photon, whose
energy is characteristic and unique to the atom of the given
element. Photons released from atoms of the material can then be
detected and identified. Each element has its own, unique x-ray
signature. A given x-ray tube can produce a continuum of x-ray
energies. The XRF analyzer can then filter out energies that are
not needed for a particular elemental analysis.
[0024] Conventional XRF analyzers cannot detect gold plating. XRF
analyzers can determine composition of gold alloys used for
manufacture of jewelry and its karatage--especially when the number
of gold alloys in use is rather small (10 to 15). XRF analysis of a
gold alloy assumes that the analyzed object is made of homogeneous
material. If the object presented for analysis by XRF is made of
brass and plated with gold, then a conventional XRF analyzer has no
means to determine the existence of gold plating. Consequently,
conventional XRF analytical software treats the object as
homogeneous. Such treatment results in erroneous analysis.
[0025] According to techniques and discoveries disclosed herein,
characteristic L-series X-rays of gold have a penetration depth in
pure and karat gold of approximately 10 to 12 micrometers (microns,
.mu.m). The two major gold lines, L-alpha and L-beta, have
different energies, 9.71 and 11.45 keV, respectively. Accordingly,
the L-alpha line is absorbed much stronger by a given medium of
gold as compared to the L-beta line. In a relatively thin layer of
pure gold that can vary its thickness (for example, from, say 0.5
.mu.m to 20 .mu.m in 1 .mu.m steps), intensities of both L-lines
can be measured. By observation, both intensities monotonically
increase with thickness of gold layer until each of them reaches
its respective "saturation" plateau at about 15 to 20 .mu.m (a self
absorption effect). Beyond this thickness of gold, there is
essentially no additional increase of intensities. Thus, absorption
of both L-lines suffers with an increased thickness of gold. Note,
however, that because the L-alpha line is less energetic, the
L-alpha line reaches its saturation plateau at faster rate than the
more energetic L-beta line. Consequently, a ratio of the two lines
at any given thickness between 0 to about 15 .mu.m is not a
constant, but instead varies with the thickness.
[0026] FIG. 2 illustrates this variation of ratio values as a
function of gold thickness. FIG. 2 shows empirical data obtained
with a hand-held XRF analyzer. Ratio values resulting from XRF
analysis of gold (Au) with no substrate are shown on the graph as
solid triangles. Ratio values resulting from XRF analysis of gold
on a copper substrate are shown on the graph as circles. Beginning
at a thickness of zero, the ratio decreases exponentially until
reaching about 12-15 microns. Once a thickness of the gold layer
exceeds a thickness of approximately 15 microns, the ratio of the
two lines does not change significantly. This ratio represents the
value for homogeneous or "infinitely" thick pure gold. Also note
that the change in ratio value is independent of having a substrate
or type of substrate. For example, similar results were discovered
when testing on a brass substrate and testing of gold foil without
a substrate. FIG. 2 also shows the relationship of an apparent
karat readout (shown with black squares) as compared to the
calculated ratio values. While karat values can be obtained using
bulk material XRF analysis, gold line ratio values can also be used
to determine an approximate karat value of an item of interest.
This apparent karat value and/or the ratio value can be used to
identify a thickness of gold plating on an object identified as
having gold plating.
[0027] The relationship between the ratio of the two lines as a
function of gold thickness can be used by an XRF analyzer as an
indicator of gold plating. In other words, this ratio and an XRF
analyzer can be used to identify counterfeit gold items. Such
identification is effective up to about a 10-12 micron thickness of
gold plating.
[0028] The XRF analyzer disclosed herein can also be used with
karat gold and karat gold plating. Gold karatage is an indication
of a percentage composition or concentration of gold in a given
gold alloy. Gold karat values use a linear system to represent
percent composition. For example, 24K gold means 100% gold, 12K
gold means 50%, and 14 karat gold means 58.3% gold. The XRF
analyzer can determine a composition of all materials in a target
object, and, based on the gold composition percentage, return a
karat value. In the jewelry trade, there are various legal gold
percentages that can be identified and sold as jewelry. For
example, some countries require at least 9 or 10 karats of gold to
qualify as a gold alloy for a solid material or plating. This means
that if gold is detected as, for example, 7 karat gold, then this
indicates that a corresponding item is not a valid gold alloy. Such
a low karat value can mean either a low gold percentage, or very
thin gold plating applied to a given, non-gold object.
[0029] 10, 12 and 14 karat gold has been commonly used in jewelry
to manufacture gold-plated articles. In practice, gold-plating of
jewelry and consumer items is rarely thicker than 8 microns. As
such, the XRF analyzer disclosed herein is well suited for
analyzing the vast majority of gold items and detecting gold
plating with high accuracy. There are various classifications of
gold plating. Gold flash is about 0.175 microns. Gold electroplate
is about 0.5 microns, and used for costume jewelry, pendants,
eyeglasses, etc. Gold plate is 1.0 microns and heavy gold plate is
2.8 microns. Gold plate and heavy gold plate are used for
bracelets, trophies, cutlery, cuff links, vermeil jewelry, medals,
etc. Specialty gold plate of 3-8 microns can be used with
liturgical items, exterior architecture, ceremonial military items,
medallions, etc. Electro-forming is 10 or more microns and used
with scientific equipment, luxury watches, and some exterior
architectural applications. Thus, most jewelry items having gold
plating are typically 1-8 microns thick, and, therefore, can be
accurately identified by the XRF analyzer disclosed herein as
plated.
[0030] Referring now to FIG. 1, a schematic illustration shows an
XRF analyzer 100 for identifying gold plating. An x-ray source 105
generates an x-ray excitation beam including photons 111A and 111B.
Photons 111A and 111B are directed onto or toward a least a portion
of an item of interest 170. Item of interest 170 includes a
substrate layer 172 and a gold plating layer 171. Note that this
combination of substrate and gold plating is exemplary. Other items
of interest could be a homogeneous gold alloy without plating.
Photons 111A and 111B can be of two different energies. Photons
111A and 111B collide with item of interest 170. These photons have
energy sufficient to eject one or more electrons from atoms of the
item of interest 170. As a consequence, atoms having electrons
ejected fluoresce by re-emission of radiation at a different energy
as shown with photons 112A and 112B. An x-ray detector 110 is
positioned to receive x-rays emitted from the item of interest. The
emitted x-rays included fluorescently emitted x-rays at a first
energy (112A) that corresponds to gold, the emitted x-rays also
included fluorescently emitted x-rays at a second energy (112B)
that corresponds to gold, that is, that corresponds to signature
characteristics of the gold atom.
[0031] A signal processor 120 is coupled to detector 110. Signals
from the detector 110 can be amplified by amplifier 115 prior to
being received at the signal processor 120. A shield 107 can
protect the detector 110 from direct radiations of source 105. The
detector 110 can detect a spectrum of photons including fluorescent
x-rays and photons from the source 105 that are scattered by the
item of interest 170. The signal processor 120 calculates a ratio
of measured intensities between an intensity of the first energy
and an intensity of the second energy (gold L-alpha line and gold
L-beta line). User interface or display 125 can then display an
indication that the item of interest is gold-plated in response to
the signal processor 120 identifying that the calculated ratio is
beyond a predetermined value.
[0032] Additional background description and use of XRF analyzers
in general can be found in U.S. Pat. No. 7,933,379, issued to
Grodzins and entitled, "Measurement of lead by X-ray fluorescence,"
which is hereby incorporated by reference.
[0033] FIG. 3 is a flow chart of logical process steps that the XRF
analyzer can execute as part of its method for identifying gold
plating. In step 310, the XRF analyzer analyzes emitted radiation
from the item of interest 170 and identifies multiple items of
information corresponding to the item of interest. This
identification includes steps that: (1) determine a percentage gold
composition (karat value), (2) determine a ratio of gold L-alpha
and gold L-beta lines, (3) determine a silver composition
(percentage/concentration), and (4) determine a nickel composition
(percentage/concentration). With these items of information
identified or calculated, the XRF analyzer can evaluate this
information to identify any gold plating. A corresponding device
can be calibrated for bulk alloy analysis to calculate all
percentages of metals.
[0034] In step 320 the XRF analyzer identifies if the gold karat
value is less than about 8 (less than 33% gold). With a gold karat
value less than about 8, the XRF analyzer then identifies in step
325 whether the silver composition is more than 20%. If the silver
composition is more than about 20% then the XRF analyzer identifies
the item of interest as either gold-plated brass or gold-plated
silver (327). If the silver composition is less than about 20% then
the XRF analyzer identifies the item of interest as gold-plated
brass (329). In other embodiments, the XRF analyzer can identify
different substrate materials, or simply identify that the
substrate is not a gold alloy or legal gold alloy. The vast
majority of gold plated jewelry items have plating on either brass
or silver, though it can be possible for gold to be plated on other
substrates. Note that the item of interest is a metallic item that
has either been represented as a gold item (such as by an
individual), or has the appearance of gold (at least on the
surface).
[0035] Gold plating can be very thin, and when combined with a
substrate may return a reading of 10% gold (2.4 karat). In this
case it is easily determined that an item of interest is not a gold
alloy because the gold percentage is too low. That is, even if the
item of interest were a solid alloy having a low percentage of gold
throughout, such a low karatage is not considered as a legal gold
alloy, and is thus a counterfeit gold alloy or a gold plated
object. In either case it can be deemed counterfeit. Note that if
the object of interest happened to be a solid alloy having, for
example, 10% gold, then this item of interest could nevertheless
have some value as an object from which gold can be extracted, but
could not be legally represented as a gold alloy or jewelry item.
This can be used as a first indication that an item of interest
being analyzed is a plated object. With such a result it is
optional whether to look at the ratio of lines because this low
karatage determination can be sufficient to conclude gold plating.
In another case, the gold content may be identified as 8 or 9
karat. At this point there needs to be more than a karatage
analysis to identify gold plating because such karatage is close to
what is allowed on the market. In this case the system then looks
to the ratio of the two lines to decide whether an item is
plated.
[0036] In step 330 the XRF analyzer identifies whether the ratio of
gold L-alpha line to gold L-beta line is more than 0.84 or less
than 0.60. That is, whether the ratio value is outside of the range
of 0.61-0.84. The ratio value can be calculated from net
intensities. With a ratio value more than 0.84 or less than 0.60,
the XRF analyzer continues to step 335. In step 335 the XRF
analyzer then identifies whether the silver composition is more
than 20%. If the silver composition is more than about 20% then the
XRF analyzer identifies the item of interest as either gold-plated
brass or gold-plated silver (337). If the silver composition is
less than about 20% then the XRF analyzer identifies the item of
interest as gold-plated brass (339). Note that some gold plated
objects can mimic a 14 karat gold piece, and so relying on a karat
analysis alone may be insufficient to accurately verify plating.
Using the ratio analysis, however, XRF analyzer can identify
seemingly 14 karat gold objects that are in reality gold-plated
objects. When gold plating thickness approaches zero thickness,
FIG. 2 teaches that the ratio of gold lines should reach a value of
approximately 1.1. However, when the plating is extremely thin,
such as less than approximately 0.2 microns, the net intensities of
gold lines are very small and as such they are measured with large
uncertainty. Consequently, the measured intensity of the first gold
line may be much smaller than the measured intensity of the second
gold line resulting in the ratio much smaller than the
predetermined value of 0.84. That is why the ratio value of 0.60
can be used as an additional technique to verify gold plating. Such
low ratios are the result of extremely thin gold plating. The exact
numerical values of the predetermined ratios are specific to a
given XRF analyzer for which they were determined. By way of a
non-limiting example, other XRF analyzers may analyze gold lines
such that a gold line ratio threshold (beyond which gold plating is
concluded) could be 0.63, 0.77, 0.86, etc. Other XRF analyzers can
use different values although it is not expected that the various
XRF analyzers will differ much from the examples described herein.
In any XRF analyzer, the basic technique is the same in that after
experimentation and/or calibration, an XRF analyzer can be
configured for detected gold plating according to its respective
x-ray detection and measurement mechanisms. Changing ratio values
can be identified until a thickness reaches about 15 microns of
gold/gold alloy, after which the ratio becomes substantially
constant.
[0037] In step 340, the XRF analyzer identifies whether the nickel
percentage composition is more than 10%. With a nickel composition
more than 10%, the XRF analyzer continues to step 345. In step 345
the XRF analyzer then identifies whether the silver composition is
more than 20%. If the silver composition is more than about 20%
then the XRF analyzer identifies the item of interest as either
gold-plated brass or gold-plated silver (347). If the silver
composition is less than about 20% then the XRF analyzer identifies
the item of interest as gold-plated brass (349). With a nickel
composition less than 10%, the XRF analyzer identifies the item as
either gold-filled, gold alloy, or otherwise recommend further
testing.
[0038] Calculating a percentage of silver or nickel can be
important because these metals are commonly used in gold alloys.
The ratio of these metals, therefore, can provide additional
certainty of an object that is plated. Legitimate plating of gold
on brass often includes a layer of nickel over the brass to prevent
the copper in the brass from diffusing into the gold plating, which
diffusion can change a plating color or corrode the plating. Silver
also has a similar tendency to diffuse into gold plating. A
Gold-filled object refers to an object with very thick gold
plating, such as substantially more than 20 microns. In such
situations more testing may be necessary because, although the item
may not be gold plated, the item could still be gold filled instead
of a bulk gold alloy.
[0039] Thus, an XRF analyzer can be used to differentiate true gold
from gold plating. Such techniques are accurate up to about 10-15
microns of gold plating thickness. Gold plating above 10-15 microns
can be sufficiently thick to attenuate x-rays coming from a
substrate on which the gold plating is applied. While gold plating
in certain items can exceed 15 microns, jewelry gold and decorative
gold items tend to be relatively thin, that is, typically less than
about 5-8 microns. With such relatively thinner gold plating, it is
possible for some x-rays to penetrate the gold plating to reflect
off of the substrate and provide for relatively quick and
nondestructive verification of gold-plating.
[0040] FIG. 4 illustrates an example block diagram of an XRF
analyzer 140 operating in a computer/network environment according
to embodiments herein. In summary, FIG. 4 shows computer system 149
displaying a graphical user interface 133 that provides an XRF
analyzer interface. Computer system hardware aspects of FIG. 4 will
be described in more detail following a description of the flow
charts.
[0041] Functionality associated with XRF analyzer 140 will now be
discussed via various embodiments. One embodiment includes a method
for identifying gold plating on objects by x-ray fluorescence
(XRF). The XRF analyzer directs an x-ray excitation beam onto at
least a portion of an item of interest such that the x-ray
excitation beam causes the item of interest to fluorescently emit
x-rays at various energies. For example, a user manipulating a
hand-held device can target a gold necklace, bracelet, ring, etc.,
so that the item of interest is in the path of emitted x-rays. The
XRF analyzer measures an intensity of a first energy that
corresponds to gold. This first energy is identified from x-rays
fluorescently emitted from the item of interest. The XRF analyzer
also measures an intensity of a second energy that corresponds to
gold. This second energy is identified from x-rays fluorescently
emitted from the item of interest. Energies corresponding to gold
refer, for example, to photon energies having an energy signature
characteristic of elemental gold. The XRF analyzer calculates a
ratio of measured intensities between the intensity of the first
energy and the intensity of the second energy. By way of a
non-limiting example, such a ratio can include gold L-alpha lines
to gold L-beta lines, that is, characteristic fluorescent emission
lines or signature lines.
[0042] In response to identifying that the calculated ratio is
beyond a predetermined value, the XRF analyzer or signal processor
can indicate via a display that the item of interest is
gold-plated. For example, a handheld scanner can emit an audible
alert, flash a light, or otherwise display text indicating that the
item of interest appears to be gold plated. If a given seller of
the item of interest represented the item of interest as a
homogenous gold alloy, but the XRF analyzer identifies the item of
interest as a gold-plated item, then an operator can conclude that
the item of interest is a counterfeit or fake gold item. Note that
the predetermined ratio value beyond which the XRF analyzer can
identify gold plating can be a ratio value relative to how the
ratio was computed. For example, example embodiments herein
calculate a ratio of gold L-alpha to gold L-beta lines. An
equivalent technique, however, would be to calculate a ratio of
gold L-beta lines to gold L-alpha lines, and then change the
threshold value accordingly, or calculate an inverse ratio,
etc.
[0043] In other embodiments, the XRF analyzer uses a value of 0.84
as the predetermined ratio value. The XRF analyzer can
alternatively identify that the calculated ratio is less than a
second predetermined value and, in response, indicate that the item
of interest is gold-plated. This second predetermined value can be
a ratio value of approximately 0.60. In other words, if the XRF
analyzer identifies that the ratio value is either more than 0.84
or less than 0.6, then the XRF analyzer can identify the item as
gold-plated.
[0044] In other embodiments, the predetermined value is a gold
lines intensity ratio representing a gold thickness of more than
about 15 microns. This gold lines intensity ratio essentially
represents gold of infinite thickness. Thus, the calculated ratio
of measured intensities (gold lines ratio measured from the item of
interest) can be compared to the gold lines intensity ratio
representing gold that is thicker than about 15-20 microns. If the
calculated ratio is about the same as the gold lines ratio for
thick gold, then the system can determine no gold plating. If,
however, there is a difference in the ratio the then XRF analyzer
can determine gold plating. An actual value of the gold lines
intensity ratio can be initially set in an XRF analyzer device, or
set after being calibrated by testing on sufficiently thick gold.
With some XRF analyzer devices this value may be about 0.84, while
other devices may different. Regardless of the particular device,
this predetermined value represents or corresponds to a gold
thickness of more that about 15 microns, which is used for
comparison to gold lines ratios observed from various gold test
objects. With a gold thickness more than about 15 microns, the
atomic properties of gold are such that when gold atoms located
deeper than about 15 microns fluoresce, the released photons from
these gold atoms are absorbed by surrounding gold atoms, thereby
preventing such photons from escaping a gold surface. Accordingly,
the calculated ratio being beyond (greater than or less then
depending on a particular calculation technique) the predetermined
value indicates a thickness of gold less that about 15 microns,
meaning that there is gold plating.
[0045] The XRF analyzer can identify a percentage composition of
gold from the item of interest relative to other elements in the
item of interest by analyzing a spectrum of x-rays fluorescently
emitted from the item of interest. In response to identifying that
the concentration of gold is less than about 33 percent, the XRF
analyzer can indicate (or confirm) that the item of interest is
gold-plated. In some embodiments, this can be a first test to
indicate gold plating. If a gold percentage is sufficiently low,
then a ratio analysis may not be necessary because the karatage is
sufficiently low such that the item of interest is either gold
plated or a fake/illegal gold alloy Likewise, the XRF analyzer can
identify a percentage composition of nickel from the item of
interest relative to other elements in the item of interest by
analyzing the spectrum of x-rays fluorescently emitted from the
item of interest. In response to identifying that the concentration
of nickel is greater than about 10 percent, the XRF analyzer can
indicate that the item of interest is gold-plated. Identifying a
percentage composition of gold and or other elements can be
executed using bulk analysis of elemental composition of the item
of interest using an energy dispersive XRF analyzer or a wavelength
dispersive XRF analyzer.
[0046] The XRF analyzer can identify a percentage composition of
silver from the item of interest relative to other elements in the
item of interest by analyzing the spectrum of x-rays fluorescently
emitted from the item of interest. In response to identifying that
the concentration of silver is less than about 20 percent, the XRF
analyzer can indicate that the item of interest is gold-plated
brass. In response to identifying that the concentration of silver
is greater than about 20 percent, the XRF analyzer can indicate
that the item of interest is either gold-plated brass or
gold-plated silver. In addition to indicating that the item of
interest is gold-plated, the XRF analyzer can indicate an
approximate thickness of gold plating on the item of interest based
on the calculated ratio of gold lines.
[0047] In another embodiment, the XRF analyzer can function
primarily as a software process for identifying gold plating on
objects from x-ray fluorescence (XRF). In such a process the XRF
analyzer can execute on an XRF device, or process XRF data
remotely. Such an embodiment includes receiving data corresponding
to x-rays that have been fluorescently emitted at various energies
from an item of interest, receiving an intensity of a first energy
that corresponds to gold, the first energy identified from x-rays
fluorescently emitted from the item of interest, receiving an
intensity of a second energy that corresponds to gold, the second
energy identified from x-rays fluorescently emitted from the item
of interest. With such data available, the XRF analyzer can then
calculate a ratio of measured intensities between the intensity of
the first energy and the intensity of the second energy. In
response to identifying that the calculated ratio is beyond a
predetermined value, the XRF analyzer can then indicate that the
item of interest is gold-plated.
[0048] In other embodiments, a ratio of copper or zinc lines can
also be considered as an additional factor in making a
determination of plating. Similar to gold, a ratio of copper lines
is also monotonic and a sharp function of plate thickness.
Accordingly, in some embodiments, the ratio of copper lines can be
used (instead of or together with the ratio of gold lines) to
determine whether an item of interest has gold plating. Relying on
gold lines instead of copper lines, however, can be more beneficial
because the relative error of measurement of the ratio of gold
lines gets smaller with plate thickness, while the relative error
of measurement of the ratio of copper lines increases with
thickness. In other words, using copper line ratios is not as
accurate as using gold line ratios because the error rate of using
copper line ratios can be deemed unacceptable. Other embodiments
can include calculating a karat value and ratio of La/LB in a given
sample (test object) and divide it by a reference ratio. If the
karat value is none of known (acceptable) karatages, then the
sample may be fake (gold plated). If a reference gold line ratio is
more than 1.03, then the object is identified as gold plated. If a
reference gold line ratio is more than 1.03 and a copper line ratio
is less than 3 but more than 1, then the object can be identified
as plated with 24K gold. If a reference gold line ratio is more
than 1.03 and a copper line ratio is more than 4.0, then the object
can be identified as plated with less than 24 K gold. If none of
the above are true, then an inconclusive indication can be given,
or otherwise direct the further testing is recommended.
[0049] In other embodiments, similar techniques can be implemented
to identify plating from other metals or materials such as to
identify silver plating versus solid silver alloy, chrome plating,
rhodium plating, platinum plating, etc. Accordingly, identifying
plating of other metals includes using x-ray fluorescence and
measuring intensities of two or more energies of a given material
or atomic element from a target item. A ratio of measured
intensities between the two or more energies can then be compared
to a predetermined value to determine plating. The predetermined
value represents a lines intensity ratio of a given specific
material/element when that specific material is essentially
infinitely thick. In other words, the lines intensity ratio
corresponds to a value that does not continue to change with
increased thickness of the given material. Because different atomic
elements have different signature characteristics, lines intensity
ratio values and curves can vary among elements. Thus, embodiments
to detect plating other than gold plating follow the same
techniques as described for detecting gold plating, but with values
and ratios modified to correspond to a specific material.
[0050] Continuing with FIG. 4, the following discussion provides a
basic embodiment indicating how to carry out functionality
associated with the XRF analyzer 140 as discussed above. It should
be noted, however, that the actual configuration for carrying out
the XRF analyzer 140 can vary depending on a respective
application. For example, computer system 149 can include one or
multiple computers that carry out the processing as described
herein.
[0051] In different embodiments, computer system 149 may be any of
various types of devices, including, but not limited to, XRF
analyzer, a cell phone, a personal computer system, desktop
computer, laptop, notebook, or netbook computer, mainframe computer
system, handheld computer, workstation, network computer, router,
network switch, bridge, application server, storage device, a
consumer electronics device such as a camera, camcorder, set top
box, mobile device, video game console, handheld video game device,
or in general any type of computing or electronic device.
[0052] Computer system 149 is shown connected to display monitor
130 for displaying a graphical user interface 133 for a user 136 to
operate using input devices 135. Repository 138 can optionally be
used for storing data files and content both before and after
processing. Input devices 135 can include one or more devices such
as a keyboard, computer mouse, microphone, etc.
[0053] As shown, computer system 149 of the present example
includes an interconnect 143 that couples a memory system 141, a
processor 142, I/O interface 144, and a communications interface
145.
[0054] I/O interface 144 provides connectivity to peripheral
devices such as input devices 135 including a computer mouse, a
keyboard, a selection tool to move a cursor, display screen,
etc.
[0055] Communications interface 145 enables the XRF analyzer 140 of
computer system 149 to communicate over a network and, if
necessary, retrieve any data required to create views, process
content, communicate with a user, etc. according to embodiments
herein.
[0056] As shown, memory system 141 is encoded with XRF analyzer
140-1 that supports functionality as discussed above and as
discussed further below. XRF analyzer 140-1 (and/or other resources
as described herein) can be embodied as software code such as data
and/or logic instructions that support processing functionality
according to different embodiments described herein.
[0057] During operation of one embodiment, processor 142 accesses
memory system 141 via the use of interconnect 143 in order to
launch, run, execute, interpret or otherwise perform the logic
instructions of the XRF analyzer 140-1. Execution of the XRF
analyzer 140-1 produces processing functionality in XRF analyzer
process 140-2. In other words, the XRF analyzer process 140-2
represents one or more portions of the XRF analyzer 140 performing
within or upon the processor 142 in the computer system 149.
[0058] It should be noted that, in addition to the XRF analyzer
process 140-2 that carries out method operations as discussed
herein, other embodiments herein include the XRF analyzer 140-1
itself (i.e., the un-executed or non-performing logic instructions
and/or data). The XRF analyzer 140-1 may be stored on a
non-transitory, tangible computer-readable storage medium including
computer readable storage media such as floppy disk, hard disk,
optical medium, etc. According to other embodiments, the XRF
analyzer 140-1 can also be stored in a memory type system such as
in firmware, read only memory (ROM), or, as in this example, as
executable code within the memory system 141.
[0059] In addition to these embodiments, it should also be noted
that other embodiments herein include the execution of the XRF
analyzer 140-1 in processor 142 as the XRF analyzer process 140-2.
Thus, those skilled in the art will understand that the computer
system 149 can include other processes and/or software and hardware
components, such as an operating system that controls allocation
and use of hardware resources, or multiple processors.
[0060] Those skilled in the art will also understand that there can
be many variations made to the operations of the techniques
explained above while still achieving the same objectives of the
invention. Such variations are intended to be covered by the scope
of this invention. As such, the foregoing description of
embodiments of the invention are not intended to be limiting.
Rather, any limitations to embodiments of the invention are
presented in the following claims.
* * * * *