FLOW CELL AND OPTICAL SYSTEM FOR ANALYZING FLUID
20200158625 ยท 2020-05-21
Inventors
Cpc classification
G01N21/01
PHYSICS
G01N2201/128
PHYSICS
International classification
Abstract
A flow cell analyzes a fluid sample. A flow cell body contains a reference material and includes at least one hollow chamber to contain the fluid sample. Opposing surfaces of the flow cell body each have at least one transparent portion thereof. An optical path for light traversing through the flow cell body is defined in part by the transparent portions. A switching mechanism adjusts the amount of the reference material in the optical path to effect switching of the flow cell between a reference measurement state and a fluid sample measurement state. The reference measurement state corresponds to a first light intensity measurement and the fluid sample measurement state corresponds to a second light intensity measurement.
Claims
1. A flow cell for analyzing a fluid sample, comprising: a first hollow chamber for containing a reference fluid, the first hollow chamber including opposing first and second transparent surfaces; a second hollow chamber for containing the fluid sample, the second hollow chamber including opposing first and second transparent surfaces; and a switching mechanism operative to move the first and second hollow chambers so as to alternately position the transparent surfaces of the first hollow chamber and the transparent surfaces of the second hollow chamber in a light path between a light source and a light detector to effect switching of the flow cell between a reference measurement state corresponding to a measurement associated with light traversing through the first hollow chamber, and a fluid sample measurement state corresponding to a measurement associated with light traversing through the second hollow chamber.
2. The flow cell of claim 1, wherein the switching mechanism is configured to translationally move the hollow chambers to effect switching between the states.
3. The flow cell of claim 1, wherein the hollow chambers are moved jointly by the switching mechanism.
4. The flow cell of claim 1, wherein when in the reference measurement state, light emitted by the light source passes at least through the first transparent surface of the first hollow chamber, the reference fluid, and the second transparent surface of the first hollow chamber, prior to reaching the light detector.
5. The flow cell of claim 1, wherein when in the fluid sample measurement state, light emitted by the light source passes at least through the first transparent surface of the second hollow chamber, the fluid sample, and the second transparent surface of the second hollow chamber, prior to reaching the light detector.
6. The flow cell of claim 1, further comprising a static lens arrangement including at least a first lens and a second lens that define an optical path, and wherein when the flow cell is in the reference measurement state, the transparent surfaces of the first hollow chamber are deployed in the optical path, and wherein when the flow cell is in the fluid sample measurement state, the transparent surfaces of the second hollow chamber are deployed in the optical path.
7. The flow cell of claim 6, wherein when the flow cell is in the reference measurement state, light emitted by the light source passes at least through the first lens, the first transparent surface of the first hollow chamber, the reference fluid, the second transparent surface of the first hollow chamber, and the second lens, prior to reaching the light detector.
8. The flow cell of claim 6, wherein when the flow cell is in the fluid sample measurement state, light emitted by the light source passes at least through the first lens, the first transparent surface of the second hollow chamber, the fluid sample, the second transparent surface of the second hollow chamber, and the second lens, prior to reaching the light detector.
9. The flow cell of claim 1, wherein when the flow cell is in the reference measurement state, the second hollow chamber is positioned out of the light path between the light source and the light detector such that substantially none of the light emitted by the light source reaches the light detector.
10. The flow cell of claim 1, wherein when the flow cell is in the fluid sample measurement state, the first hollow chamber is positioned out of the light path between the light source and the light detector such that substantially none of the light emitted by the light source reaches the light detector.
11. The flow cell of claim 1, wherein the measurement associated with light traversing through the first hollow chamber and the measurement associated with light traversing through the second hollow chamber are light intensity measurements.
12. The flow cell of claim 1, wherein the reference fluid is air.
13. The flow cell of claim 1, wherein the reference fluid is deionized water.
14. A flow cell for analyzing a fluid sample, comprising: a flow cell body including a hollow chamber for containing the fluid sample, the hollow chamber including a first surface and a second surface, the first surface fixed at a first end of the hollow chamber, and the second surface moveable relative to first surface; and a switching mechanism operative to move the second surface relative to the first surface so as to adjust an amount of the fluid sample, present in a light path extending through the hollow chamber, between at least a first fluid sample amount and a second fluid sample amount to effect switching of the flow cell between: a reference measurement state corresponding to a measurement associated with light traversing the hollow chamber, via the light path, through the first fluid sample amount, and a fluid sample measurement state corresponding to a measurement associated with light traversing the hollow chamber, via the light path, through the second fluid sample amount.
15. The flow cell of claim 14, wherein the first and second surfaces are transparent surfaces, and wherein the light path is defined in part by the first and second transparent surfaces.
16. The flow cell of claim 14, wherein the amount of the fluid sample in the light path corresponds to an amount of the fluid sample between the first and second surfaces.
17. The flow cell of claim 14, wherein the second surface is linearly moveable relative to the first surface.
18. The flow cell of claim 14, wherein movement of the second surface relative to the first surface effects a distance between the first and second surfaces, and wherein the distance is variable over a range of distances between a first distance and a second distance.
19. The flow cell of claim 14, wherein the first and second surfaces are substantially parallel to each other.
20. The flow cell of claim 14, wherein when the flow cell is in the fluid sample measurement state the first and second surfaces are separated by a first distance, and wherein when the flow cell is in the fluid sample measurement state the first and second surfaces are separated by a second distance that is less than the first distance.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0049] Some embodiments of the present invention are herein described, by way of example only, with reference to the accompanying drawings. With specific reference to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of embodiments of the invention. In this regard, the description taken with the drawings makes apparent to those skilled in the art how embodiments of the invention may be practiced.
[0050] Attention is now directed to the drawings, where like reference numerals or characters indicate corresponding or like components. In the drawings:
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0068] The present invention is directed to flow cells and optical analysis systems, that include a flow cell, for analyzing a fluid sample in a chamber of the flow cell, to determine physical properties of the fluid, such as concentration of components in the fluid, by measuring the fluid transmission.
[0069] The principles and operation of the flow cells and optical analysis systems according to present invention may be better understood with reference to the drawings accompanying the description.
[0070] The present invention is applicable to various types of fluids, including gases and various types of liquids, for example, chemical solutions made up of a solvent and solute, in which the flow cells and optical analysis systems are used to determine the concentration of the solute.
[0071] Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not necessarily limited in its application to the details of construction and the arrangement of the components and/or methods set forth in the following description and/or illustrated in the drawings and/or the examples. The invention is capable of other embodiments or of being practiced or carried out in various ways. Initially, throughout this document, references are made to directions such as, for example, front and rear, clockwise and counter clockwise, and the like. These directional references are exemplary only to illustrate the invention and embodiments thereof.
[0072] Referring now to the drawings,
[0073] In certain embodiments, the flow cell 30 is directly built into a chemical delivery piping arrangement (not shown). For example, the flow cell 30 may be provided in a circulation path formed by such a piping arrangement connected to a chemical solution tank.
[0074] The light transmission assembly 17 includes a first optical fiber 18a, a second optical fiber 18b, and a static optical assembly 22 that includes a first static lens 24a and a second static lens 24b. Within the context of this document, the term static as referred to with respect to the components of the system 10 and the flow cell 30, generally refers to components which are fixed in position and do not move. Although represented in
[0075] The lenses 24a and 24b of the optical assembly 22 can be aligned with respective transparent portions 40a and 40b of the flow cell 30, which provide entry and exit surfaces for the light to pass through the flow cell 30. The lenses 24a and 24b, together with the transparent portions of the flow cell 30, define an optical path 56 for the light from the light source 12 to pass through the flow cell 30 (i.e., a light path).
[0076] As will be discussed in further detail in subsequent sections of the present disclosure, the transparent portions 40a and 40b of the flow cell 30 may be implemented in the form of transparent windows which occupy sections or portions of oppositely disposed surfaces of the flow cell 30. Alternatively, the entirety or nearly the entirety of such oppositely disposed surfaces may be transparent. For simplicity, throughout the remainder of this document the transparent portions 40a and 40b are referred to interchangeably as transparent windows 40a and 40b. However, it should be clear that such windows are not strictly limited to minority sections or portions of the respective oppositely disposed surfaces of the flow cell 30 but may also include the entirety or nearly the entirety of the respective oppositely disposed surfaces of the flow cell 30.
[0077] The flow cell 30 includes a switching mechanism 46 for switching the flow cell 30, and the system 10, between a first measurement state and a second measurement state. Within the context of this document, the first measurement state is referred to interchangeably as a fluid sample measurement state, a sample measurement state, and the second measurement state is referred to interchangeably as a reference measurement state or a calibration state. In certain embodiments, the switching between the two states is affected by the switching mechanism 46 adjusting the amount of the reference material that is deployed in the optical path 56, which by analogy adjusts the length of the optical path traversed by the light through the flow cell 30, and by further analogy adjusts the amount of the fluid sample, or the thickness of the fluid sample, that is in the optical path 56. In certain embodiments, the reference material is a transparent rod, which in certain implementations may be constructed from a chemically stable material, for example, sapphire or quartz. It is noted that construction of such transparent rods from sapphire may provide stability to the flow cell 30 in situations in which the fluid sample under analysis is an aggressive chemical solution. In other embodiments, the reference material may be the same solvent as the fluid sample without solute, a solution made of the same solvent and an accurately known concentration of the same solute material, or a fluid of known transmittance (e.g., air or deionized water).
[0078] In general, all of the components of the system 10 are static components, with the exception of the switching mechanism 46 and components which drive the switching mechanism 46. The collimated light beam that enters the flow cell 30 is neither diverged nor converged by the flow cell 30, meaning that the light beam is either parallel or normal to all of the optical surfaces of the system 10, which includes the lenses 24a and 24b, the portions 40a and 40b, and the various surfaces of the switching mechanism 46, as will be discussed in further detail in subsequent sections of the present disclosure. However, note that other implementations are possible in which the light entering the flow cell 30 is not necessarily collimated, and the light beam impinges the optical surfaces of the system 10 at oblique angles.
[0079] The system 10 further includes a processing unit 16 coupled to the light detector 14 for executing algorithms which calculate the transmittance and concentration of the fluid sample based on signals produced by the light detector 14 in the two measurement states. The processing unit 16 includes at least one processor coupled to a storage medium, such as a memory or the like. The processor can be any number of computer processors including, but not limited to, a microprocessor, an ASIC, a DSP, an FPGA, a state machine, and a microcontroller. Such processors include, or may be in communication with computer readable media, which stores program code or instruction sets that, when executed by the processor, cause the processor to perform actions. Types of computer readable media include, but are not limited to, electronic, optical, magnetic, or other storage or transmission devices capable of providing a processor with computer readable instructions. The algorithms and calculations executed by the processing unit 16 will be described in further detail in subsequent sections of the present disclosure.
[0080] Note that the optical assembly 22, the light source 12, and the light detector 14 may be embedded together with the flow cell 30 as part of a flow cell assembly, providing direct coupling of the light source 12 and the light detector 14 to the respective lenses 24a and 24b, thereby avoiding the need for optical fibers 18a and 18b.
[0081] With continued reference to
[0082] The optical assembly 22 further includes an input arrangement 23a and an output arrangement 23b. The input arrangement 23a includes the lens 24a and a light input port 25a that receives light from the light source 12, via an input light-guiding element (e.g., optical fiber), and guides the light, through the lens 24a, to the flow cell 30. The output arrangement 23b includes the lens 24b and a light output port 25b, that receives the light, after passing through the flow cell 30 and the lens 24b, and guides the light, via an output light-guiding element (e.g., optical fiber) to the light detector 14. Note that the lens 24a may alternatively be separate from the input arrangement 23a, for example, the lens 24a may be deployed between the light source 12 and the input light-guiding element. Similarly, the lens 24b may be separate from the output arrangement 23b, for example, the lens may be deployed between the light detector 14 and the output light-guiding element.
[0083] The flow cell 30 includes a flow cell body 32 provided with oppositely disposed surfaces, namely a front surface 38a and a rear surface 38b. The flow cell 30 is deployed such that the front surface 38a is positioned proximate to the lens 24a, and the rear surface 38b is positioned proximate to the lens 24b. The front surface 38a is formed as part of a front cover 36 of the flow cell body 32.
[0084] To better demonstrate the components of the flow cell 30,
[0085] With reference to
[0086] The flow cell body 32 is further provided with an inlet port 42 and an outlet port 44 which provide a flow path for the fluid sample to flow through the hollow chamber 34 of the flow cell 30. The fluid sample is introduced into the flow cell 30 via the inlet port 42 and is expelled from the flow cell via the outlet port 44. In embodiments in which the flow cell 30 is provided in the circulation path formed by a chemical solution piping arrangement connected to a chemical solution tank, the ports 42 and 44 facilitate the flow of the fluid sample through the circulation path. In such embodiments, the inlet port 42 may receive the fluid sample from the chemical solution tank via an input portion of the chemical solution piping arrangement that is mutually connected to the chemical solution tank and the inlet port 42 at opposite ends thereof, and the outlet port 44 may provide the expelled fluid from the flow cell 30 to a sump tank (or recirculated back to the chemical solution tank) via an output portion of the chemical solution piping arrangement that is mutually connected to the sump tank (or chemical solution tank) and the outlet port 44 at opposite ends thereof.
[0087] The ports 42 and 44 may be respectively fitted with one-way valve arrangements to prevent back flow through the ports 42 and 44, ensuring unidirectional flow of the fluid sample through the flow cell 30.
[0088] In the implementation of the flow cell 30 illustrated in
[0089] As shown in
[0090] The center of gravity of the front planar surface of the base plate 49 is aligned with a central axis 54 (as seen in
[0091] Refer now to
[0092] Note that the rotation of the base plate 49 may be rotation in either a clockwise or counter clockwise direction and may be partial and/or non-continuous rotation. In a non-limiting example, in implementations in which the motor 26 is implemented as a stepper motor, the stepper motor can be controlled to allow stepped rotation in clockwise and counter clockwise directions. In another non-limiting example, the motor 26 may reach a limit switch to reverse the direction of rotation.
[0093] Although
[0094] An example construction of the rod 52 is illustrated in
[0095] Note that although the drawings show a rotational mechanism 48 having three rotatable arm sections 50, with the rods 52 attached to the arm sections 50 being of equal length, other implementations are possible, in which the rotational mechanism 48 includes one rotatable arm section having a single rod attached thereto. Alternatively, the rotational mechanism 48 may include two rotatable arm sections, with the rods attached to the arm sections being of different lengths in the dimension of the central axis 54. For example, one of the arm sections may have a 15-millimeter (mm) rod attached thereto, and the other arm section may have a 5 mm rod attached thereto. Moreover, the rotational mechanism 48 may include more than three rotatable arms, for example, six arms, with neighboring arms having rods of identical or different lengths. For example, a first arm section may have a 15 mm rod attached thereto, a second arm section neighboring the first arm section may have a 5 mm rod attached thereto, a third arm section neighboring the second arm section may have a 15 mm rod attached thereto, and so on. In this way, the length of the optical path through the fluid sample is switched according to the length of the rod positioned in the optical path.
[0096] Although the embodiments described thus far have pertained to a switching mechanism 46 implemented as a rotational mechanism 48 actuated to rotate by a motor 26, other embodiments are possible, in which the rotational mechanism 48 is actuated to rotate, at least in part, by non-motorized forces. In such embodiments, the rotational mechanism 48 may be actuated to rotate by the flow of the fluid sample through the hollow chamber 34 of the flow cell 30. For example, the rotational mechanism 48 may be designed as a turbine-like mechanism in which the arm sections 50 include contoured surfaces to accommodate flow induced rotation, or in which contoured blades, in addition to the arm sections 50, are connected to the base plate 49 to accommodate flow induced rotation. A motor, such as the motor 26, may still be utilized to stabilize the rotational speed of the rotational mechanism 48, and to support synchronization with the light detector 14.
[0097] The fluid sample measurement state corresponds to the situation in which none of the rods 52 are positioned in the optical path 56 (i.e., not aligned with the windows 40a and 40b). In this situation, only the fluid sample is positioned in the optical path 56, whereby the light beam from the light source 12 passes through the fluid sample when passing through the flow cell 30, resulting in the light beam traversing the fluid sample through a first optical path length.
[0098] The reference measurement state corresponds to when one of the rods 52 is positioned in the optical path 56 (i.e., aligned with the windows 40a and 40b), resulting in both some fluid sample and the rod 52, being positioned in the optical path 56. In this situation, both the fluid sample and a portion of the rod 52 are positioned in the optical path 56 and are traversed by the light beam from the light source 12 when the light beam passes through the flow cell 30, resulting in the light beam traversing the fluid sample through a second optical path length that is shorter than the first path length. This is due to the fact that the light beam is narrower than the cross section of the rod 52, and therefore the light beam passes through a small amount of the fluid sample in the flow cell 30 before passing in its entirety through the rod 52 and then again through a small amount of the fluid sample before exiting the flow cell 30.
[0099] By analogy, the positioning of one of the rods 52 in the optical path 56 displaces some of the fluid sample out of the optical path 56, thereby reducing the amount of the fluid sample in the optical path 56 in the reference measurement state relative to the amount of the fluid sample in the optical path 56 in the fluid sample measurement state. As such, the reference measurement state and the fluid sample measurement state correspond to different thicknesses of the fluid sample in the optical path 56.
[0100] A first light intensity measurement is conducted when the flow cell 30 is in the fluid sample measurement state, and a second light intensity measurement is conducted when the flow cell 30 is in the reference measurement state. Based on the two measurements conducted for the different optical path lengths, the transmittance and concentration of the solute of the fluid sample is calculated by the processing unit 16.
[0101] With continued reference to
[0102]
[0103] The thickness T.sub.1 of the fluid sample in the optical path 56 in the fluid sample measurement state can be analogously understood as approximately the distance between the windows 40a and 40b.
[0104]
[0105] The following paragraphs describe the calculations, performed by the algorithms executed by the processing unit 16, of the transmittance and concentration of the fluid sample based on signals produced by the light detector 14 in the two measurement states. S.sub.1 and S.sub.2 are the signal outputs of the light intensity measured by the light detector 14 when the flow cell 30 is in the fluid sample measurement state and the reference measurement state, respectively. S.sub.1 can be expressed as follows:
S.sub.1=k.sub.1I.sub.0e.sup.cT.sup.
where I.sub.0 is the intensity of the light radiation entering the optical system. Furthermore, S.sub.2 can be expressed as follows:
S.sub.2=k.sub.2I.sub.0e.sup.cT.sup.
[0106] In equations (5) and (6), k.sub.1 and k.sub.2 are proportionality constants that account for the throughput of the optical system and the response of the light detector 14 in the respective switching states. Contrary to the example described with reference to equations (2)-(4), the difference between the constants .sub.1 and .sub.2 (which multiply the right sides of equations (5) and (6), respectively) can be reduced appreciably for three main reasons. Firstly, the geometric optical path traversed by the light beam in the two states is generally the same, with negligible differences attributed to the presence of the transparent rod in the reference state. The relatively constant geometry of the optical path is due to the same optics of the optical assembly 22 being used in both measurement states. Secondly, the rods 52 can be manufactured with one or more layers of anti-reflective material coated on the faces of the rods 52 that are traversed by the light beam (i.e., normal to the central axis 54), rendering the rods 52 almost ineffective in reducing their optical throughput. Thirdly, time changes of throughput due to degradation of the optical elements have the same effect in both measurement states.
[0107] Using equations (5) and (6), and assuming for simplicity that the difference between k.sub.1 and k.sub.2 is negligible, the variable c can be solved for, namely by taking the natural logarithm of the ratio of S.sub.1/S.sub.2. Accordingly, the concentration c can be expressed as follows:
[0108] Note that in reference measurement state the reference material (i.e., rod 52) may be positioned in the optical path 56 such that substantially all of the fluid sample that was in the optical path 56 in the fluid sample measurement state is displaced by the rod 52, leaving substantially no fluid in the optical path 56 (i.e., T.sub.20). Alternatively, the reference material (i.e., rod 52) may be positioned in the optical path 56 leaving a residual amount of fluid between the ends of the rod 52 and the nearest corresponding transparent surface of the flow cell 30. Any such residual amounts of fluid will have a corresponding optical throughput, which will equally multiply the signal equations above, and will therefore cancel out in the signal ratio calculation.
[0109] Although the embodiments described thus far have pertained to a switching mechanism implemented as a rotational mechanism actuated to rotate by a motor or induced by the flow of the fluid sample through the hollow chamber 34 of the flow cell 30, other embodiments are possible, in which the switching mechanism is implemented as various other mechanism. The following sections describe several embodiments directed to various implementations of the switching mechanism 46. It is noted that for clarity and conciseness, the lenses 24a and 24b are not shown in the drawings illustrating the embodiments directed to the various implementations of the switching mechanism 46. However, it should be understood by those of ordinary skill in the art that the lenses 24a and 24b (or equivalent optical components) are present in such embodiments as well. It is further noted that according to certain embodiments, the lens 24a may be absent, for example, in embodiments in which the light source 12 is a source which produces a directional beam (e.g., a laser). Further note that in such embodiments the lens 24b may also be absent, or may be present in order to focus the light onto the light detector 14.
[0110] Refer now to
[0111] Although not shown in the drawings, the rod 60 may be connected to a motor, similar to the motor 26 illustrated in
[0112] Referring first to
[0113] Referring now to
[0114] Refer now to
[0115] Note that
[0116] Referring first to
[0117] Referring now to
[0118] Note that the linearly movable drive shaft 64 of
[0119] Refer now to
[0120] Referring first to
[0121] Referring now to
[0122] Note that the constants k.sub.1 and k.sub.2 may be better equated when using the dual rod arrangement. This is due to the same amount of light loss being imparted from the fluid samplerod interface in the two switching states.
[0123] It is noted that it may be particularly advantageous to use a transparent rod, or rods, as the reference material in embodiments in which the switching mechanism 46 is deployed inside the hollow chamber 34. The flow of the fluid sample through the hollow chamber 34, via the inlet port 42 and the outlet port 44, may act to flush and clean the end surfaces of the rod (i.e., the circular base portions) to remove any particles or materials which may build-up on the end surfaces over time.
[0124] It is noted that in all of the above described implementation of the switching mechanism 46, the relevant transparent rods (e.g., the rods 52, the rod 60, the rod 62, etc.) may be replaced by partially-transparent rods having known transmittance, or alternatively by chambers which contain the same solvent as the fluid sample without solute, a solution made of the same solvent and an accurately known concentration of the same solute material, or a fluid of known transmittance (e.g., air or deionized water). Such chambers have surfaces constructed from a material transparent in the spectrum of the light emitted by the light source 12.
[0125] Refer now to
[0126] Referring first to
[0127] Referring now to
[0128] Although the embodiments described thus far have pertained to a flow cell having a single hollow chamber that contains a fluid sample together with a reference material, in which a switching mechanism adjusts the amount of the reference material in the optical path or the amount of the fluid sample in the optical path, other embodiments are possible, in which the reference material and the fluid sample are deployed in separate chambers.
[0129] Refer now to
[0130] Referring first to
[0131] Referring now to
[0132] Although most of the embodiments described thus far have pertained to various switching mechanisms actuated, at least in part, by a motor, for example, a stepper motor, connected to a drive shaft, other embodiments are possible, in which alternative actuators and driving arrangements are used to actuate the disclosed switching mechanisms, such as, for example a pneumatic actuator (e.g., an air operated piston arrangement) or magnetic actuator or hydraulic actuator. Such actuators may also perform partial and/or non-continuous rotation or movement of the reference material in and out of the optical path.
[0133] Implementation of the system and/or device of embodiments of the invention can involve performing or completing selected tasks manually, automatically, or a combination thereof. Moreover, according to actual instrumentation and equipment of embodiments of the system and/or device of the invention, several selected tasks could be implemented by hardware, by software or by firmware or by a combination thereof using an operating system.
[0134] As used herein, the singular form, a, an and the include plural references unless the context clearly dictates otherwise.
[0135] The word exemplary is used herein to mean serving as an example, instance or illustration. Any embodiment described as exemplary is not necessarily to be construed as preferred or advantageous over other embodiments and/or to exclude the incorporation of features from other embodiments.
[0136] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or as suitable in any other described embodiment of the invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperative without those elements.
[0137] Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.