Abstract:
A circular cycloidal mass spectrometer has an outer electrode of generally circular configuration and an inner electrode having a generally circular outer periphery with an annulus for the flow of ions defined therebetween. The electrodes are structured to create an electric field therebetween. A magnetic field generator is structured to create a magnetic field oriented generally perpendicular to said electric field. An ion beam source for injecting ions into the annulus for travel therearound is provided, and an ion exit for discharge of the ions traveling in said annulus is provided with an ion collector being disposed adjacent to the ion exit. The circular cycloidal mass spectrometer may be structured to provide, under the influence of the electric field and magnetic field, a path of travel for the ion beams, which is similar to either epicycloidal or hypocycloidal curves. If desired, elliptical shapes or other suitable shapes providing a nonlinear path of ion travel may be employed. A filter may be interposed between said outer electrode and said inner electrode.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention provides a cycloidal mass spectrometer, which has inner and outer electrodes defining an annulus for passage of an electron beam therethrough and, more specifically, it provides such a cycloidal mass spectrometer, which permits a reduction in the number of electrodes and size, as compared with prior art cycloidal mass spectrometers. 
     2. Description of the Prior Art 
     The use of mass spectrometers in determining the identity and quantity of constituent materials in a gaseous, liquid or solid specimen has long been known. It has been known, in connection with such systems, to analyze the specimen under vacuum through conversion of the molecules into an ionic form, separating the ions by mass to charge ratio, and permitting the ions to bombard a detector. See, generally, U.S. Pat. Nos. 2,882,410; 3,070,951; 3,590,243; and 4,298,795. See, also, U.S. Pat. Nos. 4,882,485 and 4,952,802. 
     In general, mass spectrometers contain an ionizer inlet assembly wherein the specimen to be analyzed is received, a high vacuum chamber which cooperates with the ionizer inlet, an analyzer assembly which is disposed within the high vacuum chamber and is adapted to receive ions from the ionizer. Detector means are employed in making a determination as to the constituent components of the specimen employing mass to charge ratio as a distinguishing characteristic. By one of many known means, the molecules of the gaseous specimen contained in the ionizer are converted into ions, which are analyzed by such equipment. 
     It has been known with prior art cycloidal mass spectrometers to use a simple fixed collector and ramped electric field in looking at only one mass to charge ratio at a time. In many prior art mass spectrometer systems, regardless of whether they were of the cycloidal type or not, the ionizers were quite large and, as a result, dominated the design and specifications of the systems to be employed therewith. 
     U.S. Pat. No. 5,304,799 discloses a cycloidal mass spectrometer having a housing defining an ion trajectory volume, an electric field generator for establishing an electric field within the ion trajectory volume and an ionizer for receiving gaseous specimens to be analyzed and converting the same into ions, which travel through orthogonal electric and magnetic fields and subsequently impinge on a collector. This spectrometer was designed to have a plurality of different ions mass to charge ratios impinging on the collector generally simultaneously. It was stated that the cycloidal mass spectrometer and ionizer may be miniaturized to as provide a small readily portable instrument. 
     Cycloidal mass spectrometers belong to the so-called crossed field spectrometer group. In such spectrometers, charged particles move in magnetic and electric fields that are perpendicular to each other. In a uniform magnetic field as shown in FIG. 1, a charged particle moves in a circular path  2  determined by its mass, its charge, its speed and the magnetic field strength. The magnetic field may be established by pole pieces  3 , 4 , the magnetic field as shown is parallel to the z axis and the electrical field is perpendicular thereto. The magnetic field may be generated by either a permanent magnet or electromagnet. The cycle&#39;s frequency is determined by the time periods of the particle returning to a point in its trajectory. If a uniform electric field is imposed, normally across the magnetic field, the motion of the particle is imposed by a uniform motion rectangular to both fields as shown in FIG.  2 . In this figure, the magnetic field is parallel to the z axis and the electric field is parallel to the y axis. 
     A particle of a given mass will cross a reference plane at equivalent locations that are separated by a fixed distance, which is designated the pitch of the periodic motion. Particles with different molecular weights return at different pitches to equivalent points in their trajectory, which is the separation effect of this type of mass spectrometry. An example of such separation and travel is shown in FIG.  3 . 
     Cycloidal mass spectrometers of the prior art are generally based on the uniformity of the fields that result in a circular motion imposed by a linear motion of the charged particles. 
     The present invention focuses on field structures of a cycloidal mass spectrometer wherein the circular motion is imposed by another circular motion, thereby providing circular symmetry as shown in FIG.  4 . 
     SUMMARY OF THE INVENTION 
     The present invention has provided a number of improvements in cycloidal mass spectrometers by providing a circular cycloidal mass spectrometer having a generally circular outer electrode and an inner electrode having a generally circular outer periphery. An ion-receiving annulus is defined in between the outer electrode and the inner electrode with the electrodes being structured to create an electric field therebetween. A magnetic field generator is structured to create a magnetic field oriented generally perpendicular to the electric field. An ion beam source for introducing ions into the annulus for travel therearound is provided. An ion exit for discharge of the ion from the annulus and an ion collector for receiving the discharge ions are provided. 
     In one embodiment, the inner electrode is generally cylindrical and of solid cross-section and in another it has a hollow interior. The ion beam source and ion exit are so positioned that, with respect to the annulus, that the ions travel circumferentially, preferably, at least about 45 degrees between entry and exit to obtain the desired multiple cycloid effect. The upper limit of travel can be any desired angle. 
     The structure and applied electric and magnetic fields may be such that the ions travel in a path that is like a higher order cycloid, such as an epicycloidal or hypocycloidal path. 
     The electric field may have a plurality of concentric equal potential circular field lines, each having a potential proportionate to the distance from the center of the mass spectrometer such that the field increases with increasing distance from the center. 
     It is an object of the present invention to provide a cycloidal mass spectrometer having a circular, elliptical or other suitable configuration and providing highly efficient operation. 
     It is a further object of the present invention to provide a circular cycloidal mass spectrometer wherein the number of electrodes employed to create the electric field may be reduced as compared with prior art linear configurations. 
     It is a further object of the present invention to provide such a circular cycloidal mass spectrometer which has reduced dimensions as compared with prior art mass spectrometers. 
     It is yet another object of the present invention to provide a circular cycloidal mass spectrometer which is adapted to be employed for Fourier transform mass spectrometry. 
     It is yet another object of the present invention to eliminate the need for stacked electrically conductive plates, through the use of circular configuration, in a cycloidal mass spectrometer. 
     It is yet another object of the invention to provide such a system wherein neither the starting energy nor the starting angle of the ions influences the character of the trajectory. 
    
    
     These and other objects of the invention will be more fully understood from the following detailed description of the invention on reference to the illustrations appended hereto. 
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 represents an underlying known concept of a charged particle&#39;s circular path of movement in a uniform magnetic field. 
     FIG. 2 shows the superimposition of an electric field over a magnetic field and the motion of the particle imposed by both fields. 
     FIG. 3 illustrates a plurality of particles of different molecular weights returning at difference pitches to equivalent points of their trajectory. 
     FIG. 4 illustrates schematically an electric field and potential lines inside a capacitor between two concentric cylinders. 
     FIG. 5 is a schematic illustration of one embodiment of the present invention showing a cross-section in the x-y plane. 
     FIG. 6 is a schematic illustration of an alternate embodiment of the circular cycloidal mass spectrometer of the present invention showing a cross-section in the x-y plane. 
     FIG. 7 shows schematically an ionizing electron beam directed through the analyzer in a path generally parallel to its cylindrical axis. 
     FIG. 8 illustrates a charged particle moving in a magnetic field perpendicular to a concentric electric field within a cylindrical capacitor. 
     FIGS.  9 ( a ) and  9 ( b ) illustrate, in FIG.  9 ( a ), the physical concept of the generation of an epycycloid path of movement of ions and the resultant path as shown in FIG.  9 ( b ). 
     FIGS.  10 ( a ) and  10 ( b ) illustrate, in FIG.  10 ( a ), a physical concept of the generation of a hypocycloid path and, in FIG.  10 ( b ), the corresponding path of movement of ions. 
     FIG. 11 shows schematically a plurality of concentric electrodes to create special electric field profiles. 
     FIG. 12 shows equipotential lines in a circular electric field increasing proportional to the distance from the center. 
     FIG. 13 shows schematically a simplified alternative having an inner electrode and an annular outer electrode. 
     FIG. 14 shows schematically a plurality of ions having different mass-to-charge ratios separated within the type field shown in FIGS. 11 through 13 
     FIG. 15 illustrates schematically equipotential lines in a projection into the z-y plane. 
     FIG. 16 is a modified embodiment similar in some respects to the embodiment of FIG. 7 showing the use of a heating element. 
     FIG. 17 shows a modified embodiment of the invention having a filter plane. 
     FIG. 18 is an exploded view of a separator employable in the present invention. 
     FIG. 19 is a cross-sectional illustration taken through the separator of FIG. 18 in assembled, as contrasted with, exploded form. 
     FIG. 20 is an illustration of a cycloidal mass spectrometer, having a noncircular configuration. 
     FIG. 21 is a schematic illustration of a cross-section through the annular region in which ions travel in the y-z plane. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Referring again to FIG. 1, there is shown x-y-z coordinate axes with pole pieces  3 , 4  creating an applied magnetic field parallel to the z axis, causing a charged particle to move in circular paths  2 . The precise circular path  2  will be determined by the ion mass, charge, speed and the magnetic field strengths. 
     Referring again to FIG. 2, there is shown the same magnetic field as in FIG. 1 oriented parallel to the z axis and an electrical field oriented parallel to the y axis. The path of travel of the ions is represented by  6  and provides a plurality of closed loops such as  8  and  10 . The cyclotron frequency refers to the elapsed time periods between the particle leaving and returning to a point of its trajectory. For example, a time period t X  shows the elapsed time between the particle going from point “a” to point “b”. The distance between two equivalent points on a linear cycloid is the so-called “pitch.” During the motion from a to b in FIG. 2, the particle flew an angle in space of 360° or 2π. This corresponds to one revolution in FIG. 1 which requires the time t X  described by the inverse cyclotron frequency. 
     The time t X  does not depend on the special form and length of the trajectory, as long as the magnetic field is uniform. Any trajectory completing an angle of 360° in a plane perpendicular to the magnetic field takes the same time t X  for a given mass-to-charge ratio and a given magnetic field. Particles with different molecular weights return at different pitches. 
     As shown in FIG. 3, wherein the magnetic field is parallel to the z axis and the electric field, which is perpendicular thereto, is parallel to the y axis, a plurality of particles identified by the numbers,  44 ,  45 ,  46 ,  47  and  48  corresponding to differences in atomic mass units are travelling in relative spaced positions, while having the general path shown in FIG.  2 . These differences are due to the differences in molecular weight. 
     The magnetic fields may be generated by a permanent magnet or an electromagnet. 
     Referring to FIG. 4, there is shown schematically a plurality of concentric potential lines, such as lines  50 ,  52 ,  54 , for example, with the generally radial electric field lines such as  60 ,  62 ,  64  extending from the inner electrode  70 , which is generally of solid cross-sectional cylindrical shape and the outer concentric sleeve-like electrode  74 . This produces circular symmetry of the electric field. The inner electrode  70  has an outer generally circular circumferential face and the outer electrode  74  has an inner generally circular surface  76  with an annulus  80  defined therebetween. 
     Referring still to FIG. 4, the inner electrode  70  has a solid cylindrical configuration composed of a suitable electrically conductive, nonmagnetic material such as copper or aluminum. Spaced radially outwardly therefrom, is the annular outer electrode  74 . The distance between inner surface  76  of outer electrode  74  and outer surface  72  of inner electrode  70  providing an annular region for ion travel. 
     FIG. 5 shows schematically a structure of the type shown in FIG. 4 with the inner electrode  70  and outer electrode  74  defining an annulus  76 , which provides a path for flow of the ion beams. This view taken along the x-y plane shows an ionizer  80  providing an output of an ion beam  82 , which passes through injection electrodes  84  and travels in the path  90 , which provides repeating loops such as  92 ,  94 , and  96 . The ions emerge from the ionizer between exit electrodes  100  and are collected on ion collector  102 . In the form shown, the ion beam travels approximately 270 degrees within the annulus  76  beginning at injection electrodes  84  and ending at exit electrodes  100 . In the form of apparatus shown, the exit electrodes  100  will preferably be positioned about 45 to 315 degrees from injection electrodes  84 . It will be appreciated that, in general, it will be preferred to have the ion beam travel at least about 45 degrees within the annulus  76 . Any upper limit of ion beam travel, which achieves the desired result, can be employed. The upper limit, for example, may be substantial whole or fractional multiples of 360 degrees which can be greater than or less than 360 degrees. This permits the desired multiple cycloid effects. If desired, paths of travel greater or less than this preferred range may be employed depending on the desired number of cycloids. In this embodiment, the outer electrode  74  is connected to a source of voltage while the inner electrode  70  is connected to the electrical ground of the system. The separation function is created by the cylindrical structure of the analyzer that is a cylindrical capacitor of sufficient lend measured in the z axis (into and out of the page) to provide the ideal field between the electrodes  70 ,  74 . It, therefore, does not depend on the manner in which the ions are brought into the separator. 
     Referring to FIG.  6  and another embodiment of the invention, a substantially continuous outer electrode  110  cooperates with a hollow inner electrode  112 , which has an inner passageway  114 . An annulus  116  for flow of an ion beam is defined between the outer electrode  110  and the inner electrode  112 . In this embodiment, however, the ionizer  120  is disposed within the hollow  114  and emits ion beams between injection electrodes  124  into the annulus  116  wherein the ion beam  130  travels in a cycloidal path. The exit electrodes  136  are provided within the hollow  114  of inner electrode  112  as is the ion collector  140 . 
     Referring to FIG. 7, there is shown another arrangement of analyzer wherein the inner electrode  150  cooperates with the outer electrode  156  to define an annulus  160  therebetween for travel of the ion beam. An electron beam  164 , which is provided by a suitable ionizer (not shown), exits through an exit aperture  166  in the wall of separator  170  and impinges on the anode (not shown). The ion beam is created where the electrons travel through annulus  160  interiorly of the separator  170 . The ion beam exits through exit electrodes  180  and impinges on ion collector  182 . It will be appreciated that in this embodiment, the electron beam  164  enters in a direction generally parallel to the axis of inner electrode  150 . 
     FIG. 8 shows, schematically, a charged particle  180  positioned at a distance r from the center c of inner electrode  200 , which is at ground potential. Inner electrode  200  has a radius a and outer electrode  204  has a radius b. It is assumed that the particle is displaced from the x axis by an angle A. 
     It is preferred that the intraelectrode annular space between inner electrode  200  and outer electrode  204  be maintained at a relatively high vacuum. It has been shown mathematically that the motion created in this environment and under these conditions produces configurations closely related to epicycloids as shown by  210  in FIG.  9 ( b ) or hypocycloids  220  as shown in FIG.  10 ( b ). In considering the epicycloids as shown in FIGS.  9 ( a ) and ( b ), one might consider a point on a spoke of a wheel  222  of radius b rolling around the outer circumference  224  of a circle with a radius a in the direction shown by arrow B at an angle wt. The hypocycloids shown in ion path  230  in FIGS.  10 ( a ) and  10 ( b ), however, are generated where the wheel  230  moves along the inner surface of circle  234  having a radius a and through an angle wt in the direction shown by arrow C. The trajectories shown in FIGS.  9 ( a ) and  9 ( b ) result from the separator described above and are similar to epicycloids if the electric field accelerates the particle toward the center and hypoclycloids for the opposite field direction. 
     Referring to FIG. 11, and a special case of uniform circular symmetry, there is shown a series of concentric electrodes at the face  240  and back  242  of the cylindrical structure. For example, the face has a series of individual annular electrodes  243 ,  244 ,  246 ,  248 ,  250 ,  252  and  254 . In spaced relationship on the rear surface are a corresponding series of adjacent concentric electrodes  260 ,  264 , and  266 , which are spaced from the front face  240 . The trajectories of this embodiment approximate the epicycloids and hypocycloids with the difference being the addition of a to b for epicycloid and the subtraction of b from a in the case of the hypocycloid formulas. 
     It will be appreciated that for purposes of mass spectrometric separation, it is important to have focusing properties to reduce the effect of spread in initial energy and starting angle of the ions. Linear cycloidal mass spectrometers are double focusing as a result of the geometric properties of the linear cycloid. To achieve this effect in circular arrangement, an electric field that increases proportionately to the distance from center is employed. This results in an image of the linear cycloid that is in effect squeezed at any point, depending on the radial distance from the center. As a result, the field lines which are toward the outer portion are closer to each other. FIG. 12 shows a set of equipotential lines with uniform difference in voltage between adjacent lines. The field strength would increase with the distance from the center. Employing the electrode structure of FIG. 11, if the appropriate voltages are connected to each electrode, the type of field shown in FIG. 12 can be approximated. 
     The electrodes may be made of any suitable material such as stainless steel, for example. FIG. 13 shows a simplified alternative wherein an inner electrode  280  is spaced from an outer electrode  284 , which is an annular ring joined to separators  281 ,  282 . 
     FIG. 14 illustrates an example of how ions with different mass to charge ratios separate in this type of field with the inner electrode being represented as cylinder  280  and the outer electrode being ring  284 . It will be noted that a plurality of generally similar shapes displaced from each other, such as ion beams  290 ,  292 , and  294 , for example, are provided. This corresponds to the double-focusing properties of the standard cycloidal mass spectrometer. 
     Referring to FIG. 15, there is shown the confinement capability of the field structure. More specifically, equipotential lines in the projection into the y-z plane are shown in the groupings at  290  and  292 . The concave shape of the field retains the ions from escaping into the z direction. This effect is important for flying multiple cycloids and suggests the use of the separator as a storage device like the ion trap. The number of ions trapped in the separator can be increased by time to gain sensitivity by enrichment. On the other hand, a group of confined circulating ions can be detected by the radiation of their cyclotron frequency and the methods of Fourier transform mass spectrometry. 
     Referring to the embodiment of FIG. 16, there is shown a cycloidal mass spectrometer  300  which has an inner electrode  302 , an outer electrode  304 , and an annular ion transport passageway therebetween. The exit electrodes  310  cooperate with the ion collector  312 . The inner electrode  302  has a bore  314  therethrough which, in the form shown, contains a heating element  316 , the heater serves to clean the surfaces of undesired contaminates, absorbed gasses and water. This is particularly helpful with low level analysis. The heating element may be of any desired capacity and may be energized electrically. 
     Referring to FIG. 17, there is shown a cycloidal mass spectrometer which may be generally similar to that of FIG. 5 or FIG. 6, but has an enhancement. This embodiment has an inner electrode  330  spaced from an outer electrode  334  to define an annular region  336  within which ions may travel under the influence of the imposed electric field and magnetic field. Interposed between inner electrode  330  and outer electrode  334  is a filter plane element  340  which has a plurality of slots or openings such as  342 ,  344 ,  346 ,  348 ,  350 ,  352  and  354  and may be made of stainless steel in a foil thickness, for example. In the form shown, the starting ions  360  travel in a generally clockwise path through annular region  336  and, in those instances where the path of travel of an ion beam such as  370  coincides with an opening such as  342 , a cycloid  372  appears. See also cycloids  374 ,  376 ,  378 ,  380 . Ultimately the ion beam emerges and is received by collector  390 . It is noted that the ion beam  370  has a particular m/e with ion beams such as  392 ,  394  having 1/n·m/e≦m/e falling short of the first opening  342 . 
     As shown in the embodiment of FIGS. 18 and 19, the separator construction may have a generally spool shaped inner electrode  410  which cooperates with the outer electrode  414  to define the annular region  420  within which the ions will travel. A filter plane  421 , having a series of generally parallel slots such as  422 ,  424 ,  426 , for example, passing therethrough, is interposed and functions in a manner described in connection with FIG.  17 . The axis of rotational symmetry  425  passes through the aligned openings  430 ,  432 , in ground electrodes  440 ,  442  and passageway  454  in inner electrode  410  An ion beam entrance  450  is provided in ground electrode  440  and an ion beam exit  452  is provided in ground electrode  442 . Collector feed-through openings  460 ,  462  are provided. As best seen in FIG. 19, a collector  470  extends into annular region  420  and includes an outer conductor  472 , an inner conductor  474  and collector slits such as  476  in the outer conductor  472 . The slits in the outer conductor  472  let the ions pass to the inner conductor  474  of collector  470 . Tie overall outer diameter of the collector  470  may be on the order of 1 mm to keep disturbance of the field at a low level. 
     For convenience of disclosure herein, specific reference has been made repeatedly to cycloidal mass spectrometers having generally circular exterior configurations on the inner electrode and generally circular configuration on the outer electrode to define therebetween a generally circular, annular path for travel of the ion beam. It is not essential, however, that the configuration be circular and other nonlinear configurations, while perhaps not as advantageous economically in respect of equipment production, may be employed while obtaining substantial benefits of the present invention. As shown in FIG. 20, an inner electrode  500 , having a generally elliptical exterior configuration cooperates with an outer generally elliptical-shaped electrode  504  to define an annular region  506  which serves as the path of travel for ion beam  510 . Ionizer  520  cooperates with injection electrodes  522  to emit the ion beam  510  which, in the form shown, travels in a counter-clockwise direction preferably greater than 270° to adjacent the exit electrode  530  and ion collector  532 . 
     Referring to FIG. 21, there is shown a cross-section taken through the annular region of ion travel in the y-z plane. In the form shown, the outer electrode  548  is negative and has a plurality of curved equipotential lines, such as  550 ,  552 ,  554 . The equipotential lines have equal difference in voltage between two adjacent lines. The inner electrode  560  is positive and has a plurality of curved equipotential lines such as  562 ,  564 ,  566 . The ground electrode  570  is disposed therebetween with gaps  572 ,  574 ,  576 ,  578  separating the same. The curvature of the equipotential lines in FIG. 21 tend to keep the lines close to the center of the x axis. Ions to the right and left of center experience a force toward the center, thereby resisting ion escape in the z direction. This electrode structure also serves to avoid the number of cycloidal flown by a given ion depending upon the average distance from the center. 
     It will be appreciated, therefore, that the present invention has provided an effective cycloidal mass spectrometer of circular and other shapes, which permits the reduction in number of electrodes, reduction in size as well as cost of manufacture and may, depending on configuration, take advantage of symmetry in its functioning. As the analyzer surface is reduced, this results in less outgassing and desorption effects. Further, trajectories with many cycloids may be achieved without increasing the dimensions of the analyzer and, as a result, resolution is enhanced. 
     Whereas particular embodiments have been described hereinabove, for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details may be made without departing from the invention as defined in the appended claims.