TIME-OF-FLIGHT MASS ANALYSERS
20220415640 · 2022-12-29
Assignee
Inventors
- Christian Hock (Bremen, DE)
- Alexander Wagner (Bremen, DE)
- Hamish Stewart (Bremen, DE)
- Dmitry Grinfeld (Bremen, DE)
- Anastassios Giannakopulos (Bremen, DE)
- Wilko Balschun (Bremen, DE)
- Alexander MAKAROV (Bremen, DE)
Cpc classification
H01J49/068
ELECTRICITY
International classification
Abstract
The present invention relates to an assembly comprising a vacuum chamber and a time-of-flight mass spectrometer wherein the time-of-flight mass spectrometer is contained within the vacuum chamber. The time-of-flight mass spectrometer comprising a first electrode and a second electrode, the second electrode being spaced apart from the first electrode at a distance defining a portion of an ion-flight path therebetween. The assembly further comprising a first support for supporting the first electrode, the first support arranged between an inner surface of the vacuum chamber and the first electrode. The first support is configured to permit relative movement between at least a portion of the inner surface of the vacuum chamber and the first electrode. The inner surface of the vacuum chamber and the first electrode are thermally coupled. The present invention also relates to a multi-reflection time-of-flight mass analyser. The present invention also relates to an apparatus for out-gassing to remove contaminants from surfaces within a vacuum chamber by heating and subsequently cooling the surfaces.
Claims
1. An assembly comprising a vacuum chamber and a time-of-flight mass spectrometer, wherein the time-of-flight mass spectrometer is contained within the vacuum chamber, the time-of-flight mass spectrometer comprising: a first electrode and a second electrode, the second electrode being spaced apart from the first electrode at a distance defining a portion of an ion-flight path therebetween; the assembly comprising: a first support for supporting the first electrode, the first support arranged between an inner surface of the vacuum chamber and the first electrode; wherein the first support is configured to permit relative movement between at least a portion of the inner surface of the vacuum chamber and the first electrode; and wherein the inner surface of the vacuum chamber and the first electrode are thermally coupled.
2. The assembly of claim 1, wherein the assembly further comprises a second support for supporting the second electrode, the second support arranged between the inner surface of the vacuum chamber and the second electrode, wherein the second support is configured to permit relative movement between at least a portion of the inner surface of the vacuum chamber and the second electrode, and wherein the inner surface of the vacuum chamber and the second electrode are thermally coupled.
3. The assembly of claim 1, wherein the vacuum chamber is thermally coupled to the first and/or second electrode by one or more flexible thermal conductors.
4. The assembly of claim 4, wherein each flexible thermal conductor comprises one or more thermally conductive wires.
5. The assembly of claim 5, wherein each flexible thermal conductor comprises a first mount configured to connect the flexible thermal conductor to the respective electrode and a second mount configured to connect the flexible thermal conductor to the inner surface of the vacuum chamber, wherein the one or more thermally conductive wires extend between the first mount and the second mount, wherein the first mount and the second mount are thermally conductive.
6. The assembly of claim 6, wherein the first mount is electrically insulated from the respective electrode.
7. The assembly of claim 1, wherein the first and/or second support is thermally conductive thereby thermally coupling the inner surface of the vacuum chamber to the respective electrode.
8. The assembly of claim 1, wherein the first and/or second support comprises a surface configured to support the respective electrode thereon, wherein the surface is electrically insulative.
9. The assembly of claim 1, wherein the first and/or second support permits relative translation of the respective electrode relative to at least a portion of the inner surface of the vacuum chamber.
10. The assembly of claim 13, wherein the first and/or second support comprises one or more rotatable elements, each rotatable element having a curved surface configured to support the respective electrode thereon.
11. The assembly of claim 14, wherein each rotatable element is a ball, wherein the ball is received by a holder such that the ball is rotatable relative to the holder and wherein the holder is coupled to the inner surface of the vacuum chamber.
12. The assembly of claim 14, wherein the inner surface of the vacuum chamber comprises a complementary recess for receiving each rotatable element.
13. The assembly of claim 1, wherein the first and/or second support comprises a lubricated layer, wherein the lubricated layer is electrically insulative, wherein the first support is a first portion of the lubricated layer and the second support is a second portion of the lubricated layer, wherein the first support and the second support are integrally formed.
14. The assembly of claim 1, wherein the first and/or second support comprises a layer having a low coefficient of friction and formed of an electrically insulative material, wherein the first support is a first portion of the layer and the second support is a second portion of the layer, wherein the first support and the second support are integrally formed.
15. The assembly of claim 1, wherein the first and/or second support comprises one or more wires configured to suspend the respective electrode from the inner surface of the vacuum chamber.
16. The assembly of claim 1, wherein the first and/or second support comprises one or more springs extending between the inner surface of the vacuum chamber and the electrodes.
17. The assembly of claim 1, wherein the time-of-flight mass spectrometer is a multi-reflection time-of-flight mass spectrometer, the multi-reflection time-of flight mass analyser comprising a first ion-optical mirror comprising at least the first electrode and a second ion-optical mirror comprising at least the second electrode, the second ion-optical mirror being spaced apart from the first ion-optical mirror at a distance defining at least the portion of the ion-flight path therebetween, wherein the first ion-optical mirror comprises a first plurality of electrodes spaced apart from each other and/or wherein the second ion-optical mirror comprises a second plurality of electrodes spaced apart from each other, wherein the first electrode is the furthest electrode of the first plurality of electrodes from the second ion-optical mirror and/or wherein the second electrode is the furthest electrode of the second plurality of electrodes from the first ion-optical mirror.
18. The assembly of claim 1, wherein the time-of-flight mass spectrometer is a multi-turn time-of-flight mass spectrometer, the multi-turn time-of flight mass analyser comprising a first electrostatic sector comprising at least the first electrode and a second electrostatic sector comprising at least the second electrode, the second electrostatic sector being spaced apart from the first electrostatic sector at a distance defining at least the portion of the ion-flight path therebetween, wherein the first electrostatic sector comprises a first plurality of electrodes spaced apart from each other and/or the second electrostatic sector comprises a second plurality of electrodes spaced apart from each other, wherein the first electrode is the furthest electrode of the first plurality of electrodes from the second electrostatic sector and/or wherein the second electrode is the furthest electrode of the second plurality of electrodes from the first electrostatic sector.
19. The assembly of claim 1, wherein the first electrode has a shift in m/z ratio per Kelvin, wherein the second electrode has a shift in m/z ratio per Kelvin, the assembly further comprising a connector connected to the first electrode at a first connection point and connected to the second electrode at a second connection point, wherein the connector has a shift in m/z ratio per Kelvin, the connector defining a first length between the first and second connections points at a reference temperature; wherein the first length, the positions of the first and second connection points and the material of the connector are selected to compensate for the sum of the shift in m/z ratio per Kelvin in the first and second electrodes.
20. A multi-reflection time-of-flight mass analyser comprising: a first ion-optical mirror comprising a first electrode, the first electrode having a shift in m/z ratio per Kelvin, a second ion-optical mirror comprising a second electrode, the second electrode having a shift in m/z ratio per Kelvin, wherein the second ion-optical mirror is spaced apart from the first ion-optical mirror at a distance defining a portion of an ion-flight path therebetween; a connector connected to the first electrode at a first connection point and connected to the second electrode at a second connection point, wherein the connector has a shift in m/z ratio per Kelvin, the connector defining a first length between the first and second connection points at a reference temperature; wherein the first length, the positions of the first and second connection points and the material of the connector are selected to compensate for the sum of the shift in m/z ratio per Kelvin in the electrodes of the first and second ion-optical mirrors.
21. The assembly of claim 1, wherein the assembly further comprises: one or more cooling channels, the cooling channels arranged to cool surfaces within the vacuum chamber by transporting a cooling medium through the one or more channels; a heater arranged to heat the surfaces within the vacuum chamber; and an insulating material surrounding an outer surface of the vacuum chamber.
22. Apparatus for out-gassing to remove contaminants from surfaces within a vacuum chamber by heating and subsequently cooling the surfaces, the apparatus comprising: the vacuum chamber for housing a mass analyser; a heater arranged to heat the surfaces within the vacuum chamber; one or more cooling channels, the cooling channels arranged to cool the surfaces within the vacuum chamber by transporting a cooling medium through the one or more channels; and an insulating material surrounding an outer surface of the vacuum chamber.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0119] The invention may be put into practice in a number of ways and some embodiments will now be described by way of example only and with reference to the accompanying Figures in which:
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DETAILED DESCRIPTION
[0132]
[0133] The mr-TOF 30 is contained/housed within the vacuum chamber 20. The mr-TOF comprises an electrode arrangement 40 forming first and second opposing ion-optical mirrors 50, 60 spaced apart from each other along a distance defining a portion of the ion-flight path therebetween. The first ion-optical mirror 50 comprises a first plurality of electrodes 51 and the second ion-optical mirror 60 comprises a second plurality of electrodes 61. The first electrode 51a is the furthest electrode of the first plurality of electrodes 51 from the second ion-optical mirror 60. The second electrode 61a is the furthest electrode of the second plurality of electrodes 61 from the first ion-optical mirror 50.
[0134] The electrodes 51, 61 are elongated in their longitudinal direction. A longitudinal direction can be defined as a direction generally aligned with the longitudinal axis of the electrodes 51, 61. The transverse direction of the electrode 51, 61 is transverse (across), preferably perpendicular to the longitudinal direction of the electrode 51, 61. The first plurality of electrodes 51 and the second plurality of electrodes 61 are spaced apart from each other along a direction transverse to the longitudinal direction of the electrodes 51, 61.
[0135] The first plurality of electrodes 51 (i.e. the electrodes of the first ion-optical mirror 50) are titled relative to the second plurality of electrodes 61 (i.e the electrodes of the second ion-optical mirror 60) as described in U.S. Pat. No. 9,136,101, thereby producing a potential gradient that retards the ions' drift velocity and causes them to be reflected back in the drift dimension (the drift dimension being substantially aligned with the longitudinal dimension of the electrode 51, 61) and focused onto a detector 70. The tilting of the opposing mirrors would normally have the negative side-effect of changing the time period of ion oscillations as they travel down the drift dimension, making achievement of a good ion time-focus difficult. This is corrected with a stripe electrode 80 that alters the flight potential for a portion of the inter-mirror space, varying down the length of the electrodes of the first and second ion-optical mirrors 50, 60. Such correction or compensation electrodes 80 are also described in U.S. Pat. No. 9,136,101. The combination of the varying width of the stripe electrode 80 and variation of the spacing between the first and second ion-optical mirrors 50, 60, allows the reflection and spatial focusing of ions onto the detector 70 as well as maintaining a good time focus.
[0136] In use, the ion source 90, such as an ion trap with pulsed ion ejection, injects ions into the first plurality of electrodes 51 of the first ion-optical mirror 50 and the ions then oscillate between the first and second ion-optical mirrors 50, 60. The angle of ejection of ions from the ion source 90 and additional deflectors 100, 110 allow control of the energy of the ions in the drift direction, such that ions are directed down the length of the electrodes 51, 61 of the first and second ion-optical mirrors 50, 60 as they oscillate, producing a zig-zag trajectory. The total ion flight path is from the ion source 90 to the detector 70.
[0137]
[0138] As best shown in
[0139] In the preferred embodiment depicted in
[0140] A schematic diagram for an alternative configuration of the holder 122 of the support 120 is shown in
[0141] The ball 121 is preferably formed of or is coated with an electrically insulative material, such as a ceramic such that the ball 121 is electrically insulated from the electrode it supports. The holder 122 may be formed of, for example, a metallic material.
[0142] Similar supports 120 may be employed for the second plurality of electrodes 61, which are not shown in
[0143] As best shown in
[0144] As best shown in
[0145] In the embodiment shown in
[0146] Each flexible thermal conductor 150 may comprise a plurality of wires. The plurality of wires may be braided together to form a flexible strap 151. Preferably at least an upper surface of the plurality of wires are covered with an electrically insulative material, such as Teflon, which has been found to protect against voltage breakdown without significant impact on vacuum quality. The plurality of wires may be completely surrounded by an electrically insulative material, such as Teflon. The one or more wires may be compressed and/or merged at their termini.
[0147] Each flexible thermal conductor may comprise a first mount 152 configured to connect the flexible thermal conductor 150 to the respective electrode 51, 61 and a second mount 153 configured to connect the flexible thermal conductor to the inner surface 21 of the vacuum chamber 20. The thermally conductive wires 151 may extend between the first mount 152 and the second mount 153. The one or more wires may be compressed and/or merged at their termini into the first and/or second mounts 152, 153. For example, the first and second mounts 152, 153 may be formed of the compressed and/or merged wires. The first mount 152 and the second mount 153 are typically formed of a thermally conductive material, such as copper. The first mount 152 is preferably electrically insulated from the respective electrode 51, 61. In this arrangement, the first mount 152 is electrically insulated from the respective electrode 51, 61 by a spacer 155 arranged between the first mount 152 and the respective electrode 51, 61. The spacer 155 is referred to herein as an insulative spacer 155 and is preferably formed of an electrically insulative but thermally conductive material, such as a ceramic. Aluminium nitride may be a preferred material for the insulative spacer 155, since it has high thermal conductivity in addition to being electrically insulative.
[0148] The flexible thermal conductor 150 may be connected to the respective electrode 51, 61 using bolts/screws 156 extending through an opening 152a in the first mount 152 and extending through an opening (not shown) in the respective electrode 51, 61. The openings are preferably threaded. As shown in
[0149] The electrically insulative spacer 155 between the first mount 152 of the flexible thermal conductor 150 and respective electrode 51, 61 and the electrically insulative layer 157 around the bolt 156 prevent voltage breakdown which may otherwise occur due to electrical contact between the wires of the flexible thermal conductor 150 and the respective electrode 51, 61.
[0150] The second mount 153 may be connected using bolts/screws 158 to the inner surface of the vacuum chamber extending through an opening 153a in the second mount and a corresponding opening (not shown) in the inner surface 21 of the vacuum chamber 20.
[0151] As shown best in
[0152]
[0153] The second aspect of the invention provides a thermal compensation scheme.
[0154] The electrodes of the second aspect of the invention are configured similarly to the electrode arrangement described in accordance with the first aspect of the invention. As described above, the electrodes 51, 61 form first and second opposing ion-optical mirrors 50, 60 spaced apart from each other along a distance defining a portion of the ion-flight path therebetween. The first ion-optical mirror 50 comprises a first plurality of electrodes 51 and the second ion-optical mirror 60 comprises a second plurality of electrodes 61. The first electrode 51a is the furthest electrode of the first plurality of electrodes 51 from the second ion-optical mirror 60. The second electrode 61a is the furthest electrode of the second plurality of electrodes 61 from the first ion-optical mirror 50.
[0155] The electrodes 51, 61 are elongated in their longitudinal direction. A longitudinal direction can be defined as a direction generally aligned with the longitudinal axis of the electrode 51, 61. The transverse direction of the electrode is transverse (across), preferably perpendicular to the longitudinal direction. The first plurality of electrodes 51 and the second plurality of electrodes 61 are spaced apart from each other along a direction transverse to the longitudinal direction of the electrodes 51, 61.
[0156] A first connector 160 is connected to the first electrode 51a at a first connection point 161 and connected to the second electrode 61a at a second connection point 162. The first connector 160 is fixed to the first and second electrodes 51a, 61a at the first and second connection points 161, 162 such that the first connector 160 cannot translate relative to the electrodes 51a, 61a. The first connector 160 defines a first length between the first connection point 161 and the second connection point 162 at a reference temperature, which may be room temperature. The first connector 160 maintains the separation between the first and second electrodes 51a, 61a, which in turn maintains the separation/spacing between the first and second ion-optical mirrors 50, 60. The first connection point 161 and the second connection point 162 are fixed points on the electrodes 51a, 61a at which the first connector 160 is fixed to the electrodes 51a, 61a. The first connector 160 has corresponding points thereon corresponding to the first and second connection points 161, 162 on the electrodes 51a, 61a. In this preferred arrangement, the first connector 160 is arranged underneath the first and second electrodes and the first and second connection points 161, 162 are arranged on the lower surfaces of the electrodes 51a, 61a. The first connector 160 is connected to the first and second electrodes at the first and second connection points preferably using dowel pins received within corresponding openings in the electrodes. Alternatively, in an optional arrangement, the first connector 160 may be connected to the first and second electrodes at the first and second connection points using bolts or clamps. Although the first and second connection points 161, 162 are shown as being on the lower surfaces of the first and second electrodes 51a, 61a, respectively, they may instead be provided on outer edges of the respective electrode 51a, 61a. For example, the first connection point 161 may be on the outer edge of the first electrode 51a (i.e. on the edge extending along the longitudinal direction of the first electrode 51a that is distal from the second electrode 61). Similarly, the second connection point 162 may be on the outer edge of the second electrode 61a (i.e. on the edge extending along the longitudinal direction of the second electrode 61a that is distal from the first electrode 51a). In such an arrangement, the connector 160 may be indirectly coupled to the first and second electrodes 51a, 61a such as with one or more clamp(s) and/or mount(s). For example, as shown in
[0157] The first connector 160 has a longitudinal direction extending transverse (i.e. not parallel) to the longitudinal direction of the electrodes 51, 61 such that the connector extends across the space between the first and second ion-optical mirrors 50, 60. The longitudinal direction of the first connector 160 is arranged substantially perpendicular to the longitudinal direction of the electrodes 51 of the first ion-optical mirror 50. Substantially perpendicular refers to an angle of approximately 90°. The angle between the longitudinal direction of the electrodes 61 of the second ion-optical mirror 60 and the first connector 160 is less than 90°, preferably 85 to 89.99°, more preferably 89.90-89.98°. In this arrangement, the first connector 160 is shaped as a rod having a circular cross-section.
[0158] In the preferred arrangement shown in
[0159] The third connection point 171 is preferably aligned with the first connection point 161 along the longitudinal axis of the first electrode 51a. The fourth connection point 172 is preferably aligned with the second connection point 162 along the longitudinal axis of the second electrode 61a.
[0160] As discussed above, a change in temperature leads to expansion/contraction of the electrodes 51, 61 of the mass analyser. This in turn causes a change in the length of the flight path both within and between the spaced apart electrodes 51, 61 of the mass analyser. For example, without the connector(s) 160, 170 in place, as the electrodes expand, the flight path within the electrodes 51, 61 would increase due to the greater width of the electrodes 51, 61 and greater distance between the first and second ion-optical mirrors 50, 60. This change in flight path length in turn leads to a change in total time-of-flight for an ion and so a change in the m/z ratio of an ion detected by the mass analyser (i.e. a shift in m/z ratio per Kelvin).
[0161] However, with the connectors 160, 170 in place, this shift in m/z ratio per Kelvin is compensated for. Indeed, with the connector(s) 160, 170 in place, an increase in width of the electrodes 51, 61 due to their thermal expansion would cause the proximal edges of the spaced apart electrodes 51, 61 to approach each other thereby decreasing the distance between the first and second ion-optical mirrors 50, 60. However, thermal expansion of the connector(s) 160, 170 increases the distance between the first and second connection points 161, 612 (and third and fourth connection points 171, 172) to compensate for the increased width of the electrodes 51, 61 that would otherwise decrease the spacing between the first and second ion-optical mirrors 50, 60. Accordingly, the connector(s) 160, 170 substantially maintain the spacing between the first and second ion-optical mirrors 50, 60.
[0162] Each electrode 51, 61 therefore has a shift in m/z ratio per Kelvin that may be determined based on the thermal coefficient of expansion of the material it is formed from, its dimensions, geometry, and it's respective connection point 161, 162, 171, 172.
[0163] The material of the first and second connectors 160, 170, the positions of the first, second, third and fourth connection points 161, 162, 171, 172, the length defined by the first connector 160 between the first and second connection points 161, 162 at a reference temperature (i.e. the first length) and the length defined by the second connector 170 between the third and fourth connection points 171, 172 at the reference temperature (i.e. the second length) are selected such that the shift in m/z ratio per Kelvin of the connectors 160, 170 can compensate for the shift in m/z ratio per Kelvin of preferably all of the electrodes of the first and second plurality of electrodes 51, 61.
[0164] The compensation may be such that a sum of the shift in m/z ratio per Kelvin of the connectors 160, 170 and all of the electrodes 51, 61 of the first and second plurality of electrodes is less than ±10 ppm/K, preferably less than ±5 ppm/K, more preferably less than ±3 ppm/K, even more preferably less than ±2 ppm/K, most preferably less than ±1 ppm.
[0165] In view of the geometry of the connectors 160, 170 and the electrodes 51, 61 (i.e. as the longitudinal direction of the connectors 160, 170 extends parallel to the spacing between the first and second plurality of electrodes 51, 61 but transverse to the longitudinal direction of the electrodes 51, 61), the connectors 160, 170 are formed of a material having a lower coefficient of thermal expansion than the material used to form the electrodes 51, 61 in order to provide the thermal compensation. The thermal expansion coefficient of the connectors 16, 170 may be ≤½ the thermal expansion coefficient of the electrode(s) 51, 61, more preferably ≤⅕ the thermal expansion coefficient of the electrode(s) 51, 61, most preferably ≤ 1/10 the thermal expansion coefficient of the electrode(s) 51, 61.
[0166] Preferably, the connectors 160, 170 are formed of invar, with a thermal coefficient of expansion of approximately 1-2 ppm/K, preferably 1.2 ppm/K and/or the electrodes are formed of aluminium, with a thermal coefficient of expansion of approximately 20-30 ppm/K, preferably 25 ppm/K.
[0167] While the majority of compensation can be achieved by only considering the shift in m/z ratio per Kelvin of the electrodes of the first and second plurality of electrodes 51, 61. The material of the connectors 160, 170, the positions of the first, second, third and fourth connection points 161, 162, 171, 172, the length defined by the first connector 160 between the first and second connection points 161, 162 at a reference temperature (the first length) and the length defined by the second connector 170 between the third and fourth connection points 171, 172 at the reference temperature (the second length) may be selected to compensate for the shift in m/z ratio per Kelvin of other components of the analyser in addition to the electrodes e.g. the ion source 90, the detector 70 and/or the spacers 140 between the electrodes (electrode spacers 140) etc. All of these components will expand/contract with temperature change leading to a change in the ion-flight path therethrough and a consequent change in the m/z shift measured for an ion. Therefore, each of these components has an associated shift in m/z ratio per Kelvin that can be determined based on the thermal coefficient of expansion of the material they are formed from, their geometry and dimensions.
[0168] For example, the material of the first and second connectors 160, 170, the positions of the first, second, third and fourth connection points 161, 162, 171, 172, the length defined by the first connector 160 between the first and second connection points 161, 162 at a reference temperature and the length defined by the second connector 170 between the third and fourth connection points 171, 172 at the reference temperature may be selected such that the shift in m/z ratio per Kelvin of the connectors 160, 170 can compensate for the shift in m/z ratio per Kelvin of preferably all of the electrodes of the first and second plurality of electrodes 51, 61 and the electrode spacers 140.
[0169] The compensation may be such that a sum of the shift in m/z ratio per Kelvin of the connectors 160, 170, all of the electrodes 51, 61 of the first and second plurality of electrodes and the electrode spacers 140 is less than ±10 ppm/K, preferably less than ±5 ppm/K, more preferably less than ±3 ppm/K, even more preferably less than ±2 ppm/K, most preferably less than ±1 ppm/K.
[0170] By way of further example, the material of the first and second connectors 160, 170, the positions of the first, second, third and fourth connection points 161, 162, 171, 172, the length defined by the first connector 160 between the first and second connection points 161, 162 at a reference temperature and the length defined by the second connector 170 between the third and fourth connection points 171, 172 at the reference temperature may be selected such that the shift in m/z ratio per Kelvin of the connectors 160, 170 can compensate for the shift in m/z ratio per Kelvin of preferably all of the electrodes of the first and second plurality of electrodes 51, 61, the electrode spacers 140 and the ion source 90 and the detector 70.
[0171] The compensation may be such that a sum of the shift in m/z ratio per Kelvin of the connectors 160, 170, all of the electrodes 51, 61 of the first and second plurality of electrodes and the electrode spacers 140 is less than ±10 ppm/K, preferably less than ±5 ppm/K, more preferably less than ±3 ppm/K, even more preferably less than ±2 ppm/K, most preferably less than ±1 ppm.
[0172] As discussed above, the first plurality of electrodes 51 are tilted relative to the second plurality of electrodes 61. The angle of tilt in this arrangement may be approximately 0.02-0.1°. The length defined by the second connector 170 between the third connection point 171 and the fourth connection point 172, the positions of the third and fourth connection points 171, 172 and the material of the second connector 170 may be selected such that the angle of tilt is maintained with temperature change. Preferably, the second connector 170 is formed of the same material as the first connector 160. The length of the second connector 170 between the third and fourth connection points 171, 172 at a reference temperature (i.e. the second length) is different from the length of the first connector 160 between the first and second connection points 161, 162 at the reference temperature (i.e. the first length) to accommodate the tilt angle between the first and second plurality of electrodes 51, 61. For example, on a change in temperature, the first and second connectors 160, 170 when formed of the same material will expand/contract in proportion with each other thereby maintaining the tilt angle between the first and second plurality of electrodes 51, 61. The title angle is preferably maintained within ±0.01°, most preferably within ±0.001° after thermal expansion of the electrodes 51, 61 and connectors 160, 170. In an arrangement where the first and second connectors 160, 170 are each clamped to the outer edges of the respective electrode 51, 61, as shown in
[0173] The second connector 170 is preferably only attached to the first connector 160 via the first and second electrodes 51a, 61a. In other words, there is preferably no direct connection between the first and second connectors 160, 170. Consequently, on thermal expansion of the electrodes 51, 61 in their longitudinal direction, the spacing between the first and second connectors 160, 170 increases to accommodate this expansion thereby preventing bending of the electrodes 51, 61.
[0174] The second connector 170 may be fixed to the inner surface of the vacuum chamber at a position between the third and fourth connection points 171, 172, preferably equidistantly between the third and fourth connection points 171, 172. In this preferred arrangement, the second connector 170 is fixed to the inner surface 21 of the vacuum chamber 20 with minimal contact at a fixing point 180. For example, the second connector 170 may be fixed to the inner surface 21 of the vacuum chamber 20 with a dowel pin received in a corresponding opening in the inner surface 21 of the vacuum chamber 20. By way of a further example, the second connector 170 may be fixed to the inner surface 21 of the vacuum chamber 20 at fixing point 180 using a clamp that clamps the second connector 170 to the inner surface 21 of the vacuum chamber. The clamp may be bolted to the inner surface 21 of the vacuum chamber 20. By using a clamp, the second connector 170 may be fixed to the inner surface 21 of the vacuum chamber 20 without creating a hole or slot in the second connector 170 which may otherwise weaken the connector 170. The clamp may also allow for a more rigid connection between the second connector 170 and the inner surface 21 of the vacuum chamber 20. The clamp and the second connector 170 may be made of the same material, which may avoid/reduce stress or friction that may otherwise be generated due to differing thermal expansion/contraction of the clamp and the second connector 170. By way of example, the second connector 170 and the clamp used to fix the second connector 170 to the inner surface 21 of the vacuum chamber at the fixing point 180 may be formed of invar, with a thermal coefficient of expansion of approximately 1-2 ppm/K, preferably 1.2 ppm/K. The inner surface 21 is preferably the bottom surface of the vacuum chamber 20. The first connector 160 may move relative to the second connector 170 as a consequence of the expansion of the electrodes 51, 61 along their longitudinal direction but drift of the electrode assembly as a whole within the vacuum chamber 20 is prevented due to the connection of the second connector 170 to the inner surface 21 of the vacuum chamber 20 at the fixing point 180.
[0175] The connectors 160, 170 are preferably received within trenches (recesses or grooves) (not shown) formed within the inner surface 21 of the vacuum chamber 20, which is preferably the lower surface of the vacuum chamber. The trenches may extend along portions of the inner surface 21 of the vacuum chamber 20 underneath the electrodes 51, 61 such that the connectors 160, 170 do not contact the inner surface 21 of the vacuum chamber 20 except for at and/or around the fixing point 180 such that the fixing point 180 is not within the trenches. Accordingly, the connectors 160, 170 may not support the electrodes 51, 61. As shown in
[0176] As shown in
[0177] The features of the first and second aspects of the invention may be combined. For example,
[0178] In the arrangement of
[0179] Furthermore, as the supports 120 permit relative movement between the inner surface 21 of the vacuum chamber 20 and the electrodes 51, 61, thermal expansion/contraction of the vacuum chamber 20 does not significantly impact the thermal compensation scheme described in accordance with the second aspect of the invention. Indeed, the thermal expansion/contraction of the electrodes 51, 61 and thermal expansion/contraction of the connectors 160, 170 are not significantly affected by thermal expansion/contraction of the vacuum chamber 20. This is because the electrodes 51, 61 are supported by supports 120 that permit relative movement between the electrodes 51, 61 and the inner surface 21 of the vacuum chamber 20. The first connector 160 is not directly attached to the vacuum chamber 20. The second connector 170 is only attached to the vacuum chamber 20 by minimal contact (e.g. by a dowel pin) at a position (fixing point 180) between the first and second ion-optical mirrors 50, 60. Therefore, expansion/contraction of the vacuum chamber 20 on heating and cooling during bake-out does not lead to stress on the electrodes 51, 61 of the analyser.
[0180] As discussed above, the connectors 160, 170 may be connected to the electrodes 51, 61 via connector spacers 190 arranged therebetween such that the connectors are spaced apart from the electrodes 51, 61. The spacers 190 are formed of an electrically insulative material, such as a ceramic. The spacers 190 are positioned at the first, second, third and fourth connection points 161, 162, 171, 172. As discussed above, the connectors 160, 170 are received within trenches formed in the inner surface 21 of the vacuum chamber 20. The depth of the trenches is such that the connectors 160, 170 do not contact the inner surface of the vacuum chamber 20 except at the fixing point 180. Therefore, even though the connectors 160, 170 in this arrangement extend underneath the electrodes 51, 61, the connectors 160, 170 do not support the electrodes 51, 61. Instead, the electrodes 51, 61 may be entirely supported by the supports 120 that enable relative movement between the electrodes 51, 61 and the inner surface 21 of the vacuum chamber 20. Accordingly, the presence of the connectors 160, 170 does not reduce the functionality of the supports 120. The flexible thermal conductors 150 may have a cross-sectional area that is between 20-400 mm.sup.2, which enables efficient heat transfer without causing bending of the connectors 160, 170. One or more flexible thermal conductors 150 may be connected between the connector(s) 160, 170 and the inner surface 21 of the vacuum chamber 20 such that the flexible thermal conductors 150 enable transfer of heat between the connector(s) 160, 170 and the inner surface 21 of the vacuum chamber. It may be beneficial to employ multiple flexible thermal conductors 150 connected to each connector 160, 170, if the connectors are formed of a material having poor thermal conductivity, such as invar.
[0181]
[0182] The apparatus can be employed in the assembly of
[0183] As best shown in
[0184] The arrangement shown in
[0185] In the preferred arrangement of
[0186] The cooling channels 210 may be configured to actively cool the surfaces within the vacuum chamber 20 during use. In this preferred arrangement, the cooling medium employed is a gas (preferably air). Therefore, to achieve active cooling, a fan 240 is provided proximal to the inlet 230, 232 of each cooling channel 210 to drive the cooling medium through the respective cooling channel 210. In an alternative arrangement where a liquid coolant medium is provided, then a pump may be used instead to drive the cooling medium through the respective cooling channel 210. Normally, the flow of cooling medium through the cooling channels 210 may be restricted except when the fans 240 and/or pumps are activated.
[0187] In this preferred arrangement, a heatsink 250 is provided within each cooling channel 210, preferably downstream of the fan 240. The heatsink 250 is preferably formed of extruded aluminium or copper. The heatsink 250 may be attached to the recess/groove forming each cooling channel 210 by, for example, adhesive and/or bolts. The heatsink 250 is preferably formed of extruded aluminium or copper and is configured to receive the cooling medium flowing through the cooling channel 210 during use.
[0188] Vacuum pumps are not shown in the arrangement of
[0189] The apparatus may further comprise a controller (not shown) configured to control activation and termination of the heater (not shown) and activation and termination of the fans 240. The controller is configured to activate the fans 240 after termination of the heater. Therefore, in use when performing out-gassing to remove contaminants from surfaces within the vacuum chamber 20 (i.e. during bake-out), the controller activates the heater such that the heater heats the surfaces 21 within the vacuum chamber 20. The efficiency of heating the surfaces within the vacuum chamber 20 is improved due to use of the insulating material 220 surrounding the outer surface of the vacuum chamber 20. For example, to achieve outgassing for a mr-TOF analyser with a 20 m flight path, the heater only needs a power supply of less than 1 KW due to the improved efficiency achieved. Once the contaminants have been removed from the surfaces 21 within the vacuum chamber 20, the controller terminates operation of the heater and activates the fans 240 such that the flow of the cooling medium (in this case air) is driven through the cooling channels 210 thereby actively cooling the surfaces 21 within the vacuum chamber 20. This therefore improves the efficiency of cooling the surfaces 21 within the vacuum chamber 20 such that the time taken for out-gassing is reduced.
[0190] This assembly is also advantageous for general use of the time-of-flight mass analyser (i.e. not just during bake-out (out-gassing)). For example, the insulation 220 also protects the mass analyser from changes in temperature in the ambient air during use.
[0191] The inventive concept of the third aspect of the present invention described in accordance with
[0192] The inventive concept of the first, second and third aspects of the present invention described above may be employed together in any combination. For example, the first and third aspects may be employed together, the first and second aspects may be employed together, the second and third aspects may be employed together or all of the first, second and third aspects may be employed together.
[0193] Experimental Data
[0194] The data in Table 1 set out below demonstrates the thermal compensation achieved by an assembly employing the second aspect of the invention where the mass analyser is a mr-TOF analyser. In other words, the assembly comprised an arrangement similar to that shown in
[0195] The values for the shift in m/z per Kelvin set out in the table below were determined based on simulation of ion trajectories within the analyser system using MASIM3D software. In the table below, the electrodes 51, 61 are labelled as M0, M1, M2, M3, M4. As indicated in the table below, the electrodes 51, 61 of the first and second plurality of electrodes have the greatest impact on the total m/z shift per Kelvin. The spacers 140 between the electrodes 51, 61 have only a negligible effect on the total m/z shift per Kelvin.
[0196] In this arrangement, a connector 160 configured as shown in
TABLE-US-00001 Influence on m/z assignment Component Length/mm ppm/K Invar Rod (1.5 ppm/K) ±318 2.98 (632 total) Aluminium Electrode (22 28 2.94 ppm/K) M4 Aluminium Electrode M3 16 −1.98 Aluminium Electrode M2 16 −1.68 Aluminium Electrode M1 46 1.60 Aluminium Electrode M0 37 −1.31 AIN (4.5 ppm/K) Spacer 8 0.00 M4/M3 AIN Spacer M3/M2 8 0.19 AIN Spacer M2/M1 30 0.12 AIN Spacer M1/M0 24 −0.16 Total 2.69
[0197] It was found that by employing a connector 160 formed of invar and having a length of 678 mm between the first and second connection points would achieve complete compensation such that the total shift in m/z ratio per Kelvin is reduced to 0. (I.e. employing a connector 160 where the length of the connector 160 between its centre and the first connection point 161 was 339 mm and the length of the connector 160 between its centre and the second connection point 162 was 339 mm).
[0198]
[0199] The mr-TOF mass analyser was approximately 1 m.sup.2 in size and had a total ion flight path length of 21 m. The vacuum chamber 20 was heated with 50 W heating power over two twenty-four hour cycles. Flouranthene ion m/z was measured over the 48 hours of the experiment and its deviation from its initial value (i.e. prior to heating) was plotted. The change in temperature of the vacuum chamber 20 in Kelvin was measured by PT100 sensors mounted to the vacuum chamber 20. The vacuum chamber 20 reaches a thermal drift of nearly +2.5 K and the consequent shift in m/z ratio is +3.4 ppm. This therefore equates to a shift in m/z ratio per Kelvin of 1.4 ppm/K. There are anomalous changes in the shift in m/z ratio that occur over minutes while the heater is activate/deactivated when copper heatsinks are provided in the cooling channels 210. It is thought that this anomalous change may reflect stress on the chamber 20 being transferred to the ion-optical mirrors 50, 60 or movement due to rapid heating of the electrodes 51, 61. There is also some delay between the m/z shift peaks and the vacuum chamber temperature peaks due to the time taken for heat transfer to the electrodes 51, 61 of the ion-optical mirrors 50, 60 via the flexible thermal conductors 150.
[0200]