WO2010131007A2 - Surface coating on sampling cone of mass spectrometer - Google Patents

Surface coating on sampling cone of mass spectrometer Download PDF

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Publication number
WO2010131007A2
WO2010131007A2 PCT/GB2010/000967 GB2010000967W WO2010131007A2 WO 2010131007 A2 WO2010131007 A2 WO 2010131007A2 GB 2010000967 W GB2010000967 W GB 2010000967W WO 2010131007 A2 WO2010131007 A2 WO 2010131007A2
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WO
WIPO (PCT)
Prior art keywords
nickel
cone
carbide
chromium
mass spectrometer
Prior art date
Application number
PCT/GB2010/000967
Other languages
French (fr)
Other versions
WO2010131007A3 (en
Inventor
Gordon A. Jones
David S. Douce
Amir Farooq
Original Assignee
Micromass Uk Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB0908252.0A external-priority patent/GB0908252D0/en
Priority claimed from GB0908249A external-priority patent/GB0908249D0/en
Application filed by Micromass Uk Limited filed Critical Micromass Uk Limited
Publication of WO2010131007A2 publication Critical patent/WO2010131007A2/en
Priority to US13/294,650 priority Critical patent/US8471198B2/en
Publication of WO2010131007A3 publication Critical patent/WO2010131007A3/en
Priority to US13/922,681 priority patent/US8785843B2/en

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/067Ion lenses, apertures, skimmers

Definitions

  • the present invention relates to a surface coating or layer which is preferably provided on a sampling cone, cone-gas cone and/or extraction cone of a mass spectrometer.
  • Liquid chromatography is a method by which species from a mixture can be separated into their individual components.
  • the basic components of a liquid chromatography system are a pumping system comprising at least two solvent channels and a tube filled with stationary phase and a column onto which components are initially trapped. By adjusting the percentage composition of the solvent channels, species are released from the stationary phase to be detected by various means at the column output.
  • the inside diameters of LC columns vary widely from, for example, ⁇ 50 ⁇ m to > 4.6 mm.
  • the delivery flow rate required from the pumping system increases with the inside diameter of the column and ranges from several nanolitres per minute to several millitres per minute.
  • To produce a gradient at a flow rate of several nL/min it is often necessary to split the delivery flow rate from a liquid chromatograph.
  • the LC eluent may then pass to an Atmospheric Pressure lonisation ("API”) ion source where a range of ionisation processes may occur.
  • API Atmospheric Pressure lonisation
  • the ion source may, for example, comprise an Electrospray lonisation (“ESI”) ion source, an Atmospheric Pressure Chemical lonisation (“APCI”) ion source or an Atmospheric Pressure Photoionisation (“APPI”) ion source.
  • EI Electrospray lonisation
  • APCI Atmospheric Pressure Chemical lonisation
  • APPI Atmospheric Pressure Photoionisation
  • Electrospray lonisation is a widely used technique in mass spectrometry in which species present in a flowing solution are ionised by the application of a high voltage. Electrospray is known as a soft ionisation technique because the resulting ions typically comprise relatively large molecular weight species (e.g. peptides) which can then be detected as intact ions by a mass analyser. Electrospray lonisation can be achieved at several different flow rates ranging from several nl_/min to several ml_/min.
  • Mass spectrometers commonly comprise a sampling cone together with a cone-gas cone which forms the interface between the mass spectrometer and an ion source such as an Electrospray lonisation ion source.
  • a cone gas or curtain gas may be provided to the annulus between the inner sampling cone and the outer cone-gas cone. Ions which pass through the sampling cone are then transmitted through a first vacuum chamber and are transmitted onwardly through an extraction cone into a second vacuum chamber.
  • the sampling cone, cone-gas cone and extraction cone are made from stainless steel. Stainless steel is considered to be relatively inert and non-reactive.
  • conventional sampling cones, cone-gas cones and extraction cones need regular cleaning in order to maintain high performance.
  • sampling cone cone-gas cone and extraction cone for a mass spectrometer.
  • a mass spectrometer comprising a sampling cone and/or a cone-gas cone, wherein the sampling cone and/or the cone-gas cone comprise a first coating or surface provided on at least a portion of the sampling cone and/or the cone-gas cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • the sampling cone and/or the cone-gas cone is preferably made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ⁇ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ⁇ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
  • RTM INCONEL
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% carbon; (ii) 0.01-0.02 wt.% carbon; (iii) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06-0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon.
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03-0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3-0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0-24.0 wt.% chromium; (xiii) 24.0-25.0 wt.%
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% nickel; (ii) 1.0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (v) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0- 11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (xv) 14.0-15.0 wt.% nickel; (xvi) 15.0-16.0
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0- 3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
  • the sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0- 4.0 wt.% X; and (v) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
  • the sampling cone and/or the cone-gas cone preferably forms an interface between an atmospheric pressure ion source and a first vacuum chamber of the mass spectrometer.
  • the sampling cone preferably comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
  • the first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the first or inner conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the first or inner conical or frusto- conical body.
  • the cone-gas cone preferably comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture through which a cone gas emerges, in use, and wherein the second orifice or annular aperture substantially circumscribes at least part or substantially the whole of the first orifice or circular aperture.
  • the first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the second or outer conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the second or outer conical or frusto-conical body.
  • the extraction cone preferably comprises a first coating or surface provided on at least a portion of the extraction cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • the extraction cone is preferably made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ⁇ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ⁇ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
  • RTM INCONEL
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% carbon; (H) 0.01-0.02 wt.% carbon; (iii) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06-0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon. >
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03- 0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3-0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0-24.0 wt.% chromium; (xiii) 24.0-25.0 wt.% chromium; (xi
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% nickel; (ii) 1.0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (v) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0-11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (xv) 14.0- 15.0 wt.% nickel; (xvi) 15.0-16.0 wt.% nickel; (
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0-3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
  • the extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0-4.0 wt.% X; and (v) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
  • the extraction cone preferably forms an interface between a first or further vacuum chamber of the mass spectrometer and a second or further vacuum chamber of the mass spectrometer.
  • the extraction cone preferably comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
  • the first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the first or inner conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the first or inner conical or frusto- conical body.
  • the extraction cone preferably further comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture, wherein the second orifice or annular aperture substantially circumscribes at least part or substantially the whole of the first orifice or circular aperture.
  • the first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the second or outer conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the second or outer conical or frusto-conical body.
  • the first coating or surface is preferably selected from the group consisting of: (i) aluminium carbide Or AI 4 C 3 ; (ii) chromium carbide, CrC, Cr 23 C 6 , Cr 3 C, Cr 7 C 3 Or Cr 3 C 2 ; (Ni) copper carbide; (iv) hafnium carbide, HfC or HfCc 99 ; (v) iron carbide, Fe 3 C, Fe 7 C 3 or Fe 2 C; (vi) iridium carbide; (vii) manganese carbide, MnC or Mn 23 C 6 ; (viii) molybdenum carbide, Mo 2 C or Mo 3 C 2 ; (ix) nickel carbide or NiC; (x) niobium carbide, NbC, Nb 2 C, NbC 099 , or Nb 4 C 3 ; (xi) osmium carbide; (xii) palladium carbide; (xiii) platinum carbide; (xiv) rhen
  • the first coating or surface preferably comprises: (i) a transition metal carbide; (ii) a carbide alloy; or (iii) a mixed metal carbide alloy.
  • the first coating or surface preferably has either:
  • a resistivity selected from the group consisting of: (i) ⁇ 10 "3 ⁇ -m; (ii) ⁇ 10 "4 ⁇ -m; (iii) ⁇ 10 5 ⁇ -m; (iv) ⁇ 10 "6 ⁇ -m; (v) ⁇ 10 "7 ⁇ -m; (vi) lO ⁇ -W 4 ⁇ -m; (vii) 10 ⁇ -1O 5 ⁇ -m; (viii) lO ⁇ -IO "6 ⁇ -m; and (ix) lO ⁇ -IO 7 ⁇ -m; and/or
  • a Vickers hardness number or Vickers Pyramid Number selected from the group consisting of: (i) > 1000; (ii) 1000-1100; (iii) 1100-1200; (iv) 1200-1300; (v) 1300- 1400; (vi) 1400-1500; (vii) 1500-1600; (viii) 1600-1700; (ix) 1700-1800; (x) 1800-1900; (xi) 1900-2000; (xii) 2000-2100; (xiii) 2100-2200; (xiv) 2200-2300; (xv) 2300-2400; (xvi) 2400- 2500; (xvii) 2500-2600; (xviii) 2600-2700; (xix) 2700-2800; (xx) 2800-2900; (xxi) 2900- 3000; (xxii) 3000-3100; (xxiii) 3100-3200; (xxiv) 3200-3300; (xv) 3300-3400; (xvi) 3400
  • a thickness selected from the group consisting of: (i) ⁇ 1 ⁇ m; (ii) 1-2 ⁇ m; (iii) 2-3 ⁇ m; (iv) 3-4 ⁇ m; (v) 4-5 ⁇ m; (vi) 5-6 ⁇ m; (vii) 6-7 ⁇ m; (viii) 7-8 ⁇ m; (ix) 8-9 ⁇ m; (x) 9-10 ⁇ m; (xi) > 10 ⁇ m; and/or
  • a method of mass spectrometry comprising: passing ions through a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein the sampling cone and/or the cone-gas cone comprises a first coating or surface provided on at least a portion of the sampling cone and/or the cone-gas cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • a method of mass spectrometry comprising: passing ions through an extraction cone of a mass spectrometer, wherein the extraction cone comprises a first coating or surface provided on at least a portion of the extraction cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • a method of making a sampling cone and/or a cone-gas cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • a method of making an extraction cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of an extraction cone of a mass spectrometer, wherein the first coating or surface comprises a metallic carbide coating or surface.
  • the step of depositing, sputtering or forming the first coating or surface preferably comprises using a method selected from the group consisting of: (i) magnetron sputtering; (ii) closed field unbalanced magnetron sputter ion plating; (iii) electroplating; (iv) thermal spray coating; (v) vapour deposition; (vi) Chemical Vapour Deposition ("CVD”); (vii) combustion torch/flame spraying; (viii) electric arc spraying; (ix) plasma spraying; (x) ion plating; (xi) ion implantation; (xii) sputtering; (xiii) sputter deposition; (xiv) laser surface alloying; (xv) Physical Vapour Deposition ("PVD”); (xvi) plasma-based ion plating; (xvii) gas plasma discharge sputtering; (xviii) laser cladding; (xix) plasma enhanced Chemical Vapour Deposition; (xx)
  • a surface coating or a surface modification is preferably used to passivate the surfaces associated with an Atmospheric Pressure lonisation ("API") ion source region and in particular the sampling cone and/or cone-gas cone and/or extraction cone of a mass spectrometer.
  • API Atmospheric Pressure lonisation
  • the preferred surface coating or surface modification preferably improves the robustness of the sampling cone and/or cone-gas cone and/or extraction cone by reducing surface reactions with ions and/or molecules as ions flow from an atmospheric pressure region to the vacuum chambers of a mass spectrometer.
  • the improved sampling cone and/or cone-gas cone and/or extraction cone preferably has a greater durability, greater resistance to scratching, provides a robust inert surface that reduces the decomposition of contaminants, solvents, and unwanted compounds and is readily cleaned (chemically) without damage or degradation to the inert surface character.
  • the preferred sampling cone and/or cone-gas cone and/or extraction cone preferably exhibits improved performance characteristics when compared with conventional stainless steel sampling cones, cone-gas cones and extraction cones.
  • the coated surface preferably advantageously reduces adsorption of material on contact with the surface since if material is deposited onto the surface of the sampling cone, cone-gas cone or extraction cone then it may result in a reduction in signal transmission and may cause an increase in the noise.
  • Comparative data is presented which shows the differences in intensity and peak area which are observed when using a newly cleaned stainless steel sampling cone/skimmer cone, an aged (or used) stainless steel sampling cone/skimmer cone and an aged (or used) sampling cone/skimmer cone which has been adapted according to the preferred embodiment to have a surface coating.
  • the sampling cone/skimmer cone according to the preferred embodiment maintains its signal transmission while slightly increasing its noise levels (after an extended time period of intermittent use) relative to the cleaned stainless steel sampling cone/skimmer cone.
  • the aged or used stainless steel sampling cone/skimmer cone drops by a greater amount (after an extended time period of intermittent use) and the noise level also increases more significantly.
  • a sampling cone, skimmer cone and cone- gas cone which have a surface coating according to the preferred embodiment only require an organic/acid wash whereas a conventional stainless steel sampling cone, congas cone and extraction cone may require abrasive cleaning.
  • Fig. 1 shows the initial vacuum stages of a mass spectrometer comprising a sampling cone and a cone-gas cone at the entrance to a first vacuum chamber;
  • Fig. 2 shows the signal intensity factor difference obtained according to an embodiment of the present invention comparing the intensity of ion signals relating to six compounds obtained using cleaned stainless steel sampling and extraction cones and sampling and extraction cones coated with titanium carbide against an aged stainless steel cone set which was assigned a unity factor;
  • Fig. 3 shows the signal intensity factor difference for the data shown in Fig. 2;
  • Fig. 4 shows the peak area factor difference for each of the six compounds with the aged stainless steel cone set being assigned a unity factor
  • Fig. 5 shows a table of the signal to noise factor difference for the six compounds with the aged stainless steel cone set being assigned a unity factor.
  • Fig. 1 shows the initial vacuum stages of a mass spectrometer and an Electrospray capillary 1 which forms part of an Electrospray ion source which emits, in use, an ion plume 2.
  • Ions and neutral gas molecules are drawn through a sampling cone 3 into the first vacuum chamber 6 of a mass spectrometer.
  • a cone-gas cone 4 surrounds the sampling cone 3 and a cone gas or curtain gas 5 is preferably supplied to the cone-gas cone 4.
  • Neutral gas molecules continue through the first vacuum chamber 6 which is preferably evacuated by a rough pump 7 such as a rotary pump or scroll pump.
  • the rough pump, rotary pump or scroll pump serves to provide the backing pressure to a second vacuum chamber 9 which is preferably pumped by a fine pump such as a turbomolecular pump or diffusion pump.
  • the term "backing pressure" refers to the pressure in the first vacuum chamber 6. Ions are preferably diverted in an orthogonal direction by an electric field or extraction lens into the second vacuum chamber
  • Ions preferably pass through an extraction cone 8 as they pass from the first vacuum chamber 6 into the second vacuum chamber 9.
  • An ion guide 11 is preferably provided in the second vacuum chamber 9 which preferably guides ions through the second vacuum chamber 9 and which preferably onwardly transmits ions to subsequent lower pressure vacuum chambers.
  • the second vacuum chamber 9 is preferably pumped by a turbomolecular pump or a diffusion pump
  • Ions exiting the second vacuum chamber 9 preferably pass through a differential pumping aperture 12 into subsequent stages of the mass spectrometer.
  • the backing pressure or the pressure in the first vacuum chamber 6 may be maintained, in use, in the range 5 to 9 mbar.
  • the cone-gas cone 4 and the sampling cone 3 of the mass spectrometer may be maintained at a potential of 175 V.
  • the cone-gas cone 4 and the sampling cone 3 preferably comprise two co-axial cones which are preferably in direct contact with each other and which are preferably maintained at the same potential.
  • a six component mixture of different compounds namely sulphadimethoxine, verapamil, caffeine, acetominophen, chloramphenicol and 17 ⁇ hydroxyprogesterone were analysed.
  • a liquid chromatography column (for chromatographic separation) with a tandem quadrupole mass spectrometer was used to produce the resulting data.
  • the six compound mixture was analysed by positive and negative ion Electrospray ionisation (ESI+/ ESI-) using a liquid chromatography column (for chromatographic separation) with a tandem quadrupole mass spectrometer.
  • ESI+/ ESI- positive and negative ion Electrospray ionisation
  • Data was acquired using: (i) a conventional stainless steel (SS) sampling and extraction cone; (ii) a sampling and extraction cone coated with titanium carbide (TiC) according to an embodiment of the present invention; and (iii) a cleaned stainless steel (SS) sampling and extraction cone.
  • SS stainless steel
  • the stainless steel and titanium carbide sampling and extraction cones were used for an extended time period to investigate their robustness characteristics.
  • Figs. 2 and 3 show a comparison of the average intensities observed for each of the six compounds when using a used or aged stainless steel sampling and extraction cone set up, a used or aged sampling and extraction cone coated with titanium carbide (TiC) according to an embodiment of the present invention, and a recently cleaned stainless steel sampling and extraction cone.
  • TiC titanium carbide
  • Fig. 4 shows a comparison of the average areas observed for each of the six compounds when using a used or aged stainless steel sampling and extraction cone set up, a used or aged sampling and extraction cone set up coated with titanium carbide (TiC) according to an embodiment of the present invention and a recently cleaned stainless steel sampling and extraction cone.
  • TiC titanium carbide
  • Fig. 5 shows the Signal to Noise factor of an aged or used stainless steel sample and extraction cone, an aged or used TiC sampling and extraction cone according to the preferred embodiment and a cleaned stainless steel sampling and extraction cone.
  • an improvement in robustness was observed using an extraction and sampling cone coated with titanium carbide according to an embodiment of the present invention.
  • the coated surface maintains a higher signal intensity and lower noise response compared to the aged stainless steel environment for all compounds investigated. Cleaning the stainless steel surface regenerated the sample response and lowered the noise response resulting in equivalent results to the aged TiC.

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  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

A sampling cone (3) of a mass spectrometer is disclosed having a metallic carbide coating such as titanium carbide.

Description

SURFACE COATING ON SAMPLING CONE OF MASS SPECTROMETER
This application claims priority to and benefit of U.S. Provisional Patent Application Serial No. US 61/181 ,367 filed on 27 May 2009, U.S. Provisional Patent Application Serial No. US 61/181,372 filed on 27 May 2009, United Kingdom Patent Application No. 0908249.6 filed on 13 May 2009 and United Kingdom Patent Application No. 0908252.0 filed on 13 May 2009. The entire contents of these applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a surface coating or layer which is preferably provided on a sampling cone, cone-gas cone and/or extraction cone of a mass spectrometer.
Mass spectrometers comprising a Liquid chromatography ion source are well known. Liquid chromatography is a method by which species from a mixture can be separated into their individual components. The basic components of a liquid chromatography system are a pumping system comprising at least two solvent channels and a tube filled with stationary phase and a column onto which components are initially trapped. By adjusting the percentage composition of the solvent channels, species are released from the stationary phase to be detected by various means at the column output.
The inside diameters of LC columns vary widely from, for example, <50 μm to > 4.6 mm. The delivery flow rate required from the pumping system increases with the inside diameter of the column and ranges from several nanolitres per minute to several millitres per minute. To produce a gradient at a flow rate of several nL/min it is often necessary to split the delivery flow rate from a liquid chromatograph. The LC eluent may then pass to an Atmospheric Pressure lonisation ("API") ion source where a range of ionisation processes may occur. The ion source may, for example, comprise an Electrospray lonisation ("ESI") ion source, an Atmospheric Pressure Chemical lonisation ("APCI") ion source or an Atmospheric Pressure Photoionisation ("APPI") ion source.
Electrospray lonisation is a widely used technique in mass spectrometry in which species present in a flowing solution are ionised by the application of a high voltage. Electrospray is known as a soft ionisation technique because the resulting ions typically comprise relatively large molecular weight species (e.g. peptides) which can then be detected as intact ions by a mass analyser. Electrospray lonisation can be achieved at several different flow rates ranging from several nl_/min to several ml_/min. The ion counts observed in a mass spectrometer during Electrospray lonisation are not, to a first approximation, flow rate dependent and as such large sensitivity gains for the same signal to noise ratios can be achieved at lower flow rates due to much lower sample consumption.
The coupling of liquid chromatography and Electrospray mass spectrometry (LCMS) and tandem mass spectrometry (LCMS/MS) is a powerful technique that is widely used in many laboratories. Mass spectrometers commonly comprise a sampling cone together with a cone-gas cone which forms the interface between the mass spectrometer and an ion source such as an Electrospray lonisation ion source. A cone gas or curtain gas may be provided to the annulus between the inner sampling cone and the outer cone-gas cone. Ions which pass through the sampling cone are then transmitted through a first vacuum chamber and are transmitted onwardly through an extraction cone into a second vacuum chamber. Conventionally, the sampling cone, cone-gas cone and extraction cone are made from stainless steel. Stainless steel is considered to be relatively inert and non-reactive. However, conventional sampling cones, cone-gas cones and extraction cones need regular cleaning in order to maintain high performance.
Conventional sampling cones, cone-gas cones and extraction cones can suffer from increased surface contamination following regular analysis of complex matrix extracts such as urine, saliva, plasma, whole blood, waters and soils. In addition complex buffered eluent systems such as ammonium acetate, ammonium formate, sodium phosphate, sodium borate and sodium formate can also cause contamination. Other potential additives which can increase surface activity and/or contamination include formic acid, trifluoroacetic acid and ammonia.
It is desired to provide an improved sampling cone, cone-gas cone and extraction cone for a mass spectrometer. In particular, it is desired to provide a more robust sampling cone, cone-gas cone and extraction cone which is less reactive than stainless steel and which requires less intensive cleaning than conventional sampling cones, cone- gas cones and extraction cones.
SUMMARY OF THE INVENTION
According to an aspect of the present invention there is provided a mass spectrometer comprising a sampling cone and/or a cone-gas cone, wherein the sampling cone and/or the cone-gas cone comprise a first coating or surface provided on at least a portion of the sampling cone and/or the cone-gas cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
The sampling cone and/or the cone-gas cone is preferably made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ≥ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ≥ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% carbon; (ii) 0.01-0.02 wt.% carbon; (iii) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06-0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03-0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3-0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0-24.0 wt.% chromium; (xiii) 24.0-25.0 wt.% chromium; (xiv) 25.0-26.0 wt.% chromium; (xv) 26.0-27.0 wt.% chromium; (xvi) 27.0-28.0 wt.% chromium; (xvii) 28.0-29.0 wt.% chromium; (xviii) 29.0-30.0 wt.% chromium; and (xix) > 30.0 wt.% chromium.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% nickel; (ii) 1.0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (v) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0- 11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (xv) 14.0-15.0 wt.% nickel; (xvi) 15.0-16.0 wt.% nickel; (xvii) 16.0-17.0 wt.% nickel; (xviii) 17.0-18.0 wt.% nickel; (xix) 18.0-19.0 wt.% nickel; (xx) 19.0-20.0 wt.% nickel; (xxi) 20.0-21.0 wt.% nickel; (xxii) 21.0-22.0 wt.% nickel; (xxiii) 22.0-23.0 wt.% nickel; (xxiv) 23.0-24.0 wt.% nickel; (xxv) 24.0-25.0 wt.% nickel; (xxvi) 25.0-26.0 wt.% nickel; (xxvii) 26.0-27.0 wt.% nickel; (xxviii) 27.0-28.0 wt.% nickel; (xxix) 28.0-29.0 wt.% nickel; (xxx) 29.0-30.0 wt.% nickel; (xxxi) 30.0-31.0 wt.% nickel; (xxxii) 31.0-32.0 wt.% nickel; (xxxiii) 32.0-33.0 wt.% nickel; (xxxiv) 33.0-34.0 wt.% nickel; (xxxv) 34.0-35.0 wt.% nickel; (xxxvi) 35.0-36.0 wt.% nickel; (xxxvii) 36.0-37.0 wt.% nickel; (xxxviii) 37.0-38.0 wt.% nickel; (xxxix) 38.0-39.0 wt.% nickel; (xl) 39.0-40.0 wt.% nickel; (xii) 40.0-41.0 wt.% nickel; (xiii) 41.0-42.0 wt.% nickel; (xliii) 42.0-43.0 wt.% nickel; (xliv) 43.0-44.0 wt.% nickel; (xiv) 44.0-45.0 wt.% nickel; (xlvi) 45.0-46.0 wt.% nickel; (xlvii) > 46.0 wt.% nickel.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0- 3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
The sampling cone and/or the cone-gas cone preferably comprises stainless steel or an alloy comprising: (i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0- 4.0 wt.% X; and (v) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
The sampling cone and/or the cone-gas cone preferably forms an interface between an atmospheric pressure ion source and a first vacuum chamber of the mass spectrometer.
The sampling cone preferably comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
The first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the first or inner conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the first or inner conical or frusto- conical body.
The cone-gas cone preferably comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture through which a cone gas emerges, in use, and wherein the second orifice or annular aperture substantially circumscribes at least part or substantially the whole of the first orifice or circular aperture.
The first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the second or outer conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the second or outer conical or frusto-conical body.
The extraction cone preferably comprises a first coating or surface provided on at least a portion of the extraction cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
The extraction cone is preferably made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ≥ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ≥ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% carbon; (H) 0.01-0.02 wt.% carbon; (iii) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06-0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon. >
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03- 0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3-0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0-24.0 wt.% chromium; (xiii) 24.0-25.0 wt.% chromium; (xiv) 25.0-26.0 wt.% chromium; (xv) 26.0- 27.0 wt.% chromium; (xvi) 27.0-28.0 wt.% chromium; (xvii) 28.0-29.0 wt.% chromium; (xviii) 29.0-30.0 wt.% chromium; and (xix) > 30.0 wt.% chromium.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% nickel; (ii) 1.0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (v) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0-11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (xv) 14.0- 15.0 wt.% nickel; (xvi) 15.0-16.0 wt.% nickel; (xvii) 16.0-17.0 wt.% nickel; (xviii) 17.0-18.0 wt.% nickel; (xix) 18.0-19.0 wt.% nickel; (xx) 19.0-20.0 wt.% nickel; (xxi) 20.0-21.0 wt.% nickel; (xxii) 21.0-22.0 wt.% nickel; (xxiii) 22.0-23.0 wt.% nickel; (xxiv) 23.0-24.0 wt.% nickel; (xxv) 24.0-25.0 wt.% nickel; (xxvi) 25.0-26.0 wt.% nickel; (xxvii) 26.0-27.0 wt.% nickel; (xxviii) 27.0-28.0 wt.% nickel; (xxix) 28.0-29.0 wt.% nickel; (xxx) 29.0-30.0 wt.% nickel; (xxxi) 30.0-31.0 wt.% nickel; (xxxii) 31.0-32.0 wt.% nickel; (xxxiii) 32.0-33.0 wt.% nickel; (xxxiv) 33.0-34.0 wt.% nickel; (xxxv) 34.0-35.0 wt.% nickel; (xxxvi) 35.0-36.0 wt.% nickel; (xxxvii) 36.0-37.0 wt.% nickel; (xxxviii) 37.0-38.0 wt.% nickel; (xxxix) 38.0-39.0 wt.% nickel; (xl) 39.0-40.0 wt.% nickel; (xii) 40.0-41.0 wt.% nickel; (xiii) 41.0-42.0 wt.% nickel; (xliii) 42.0-43.0 wt.% nickel; (xliv) 43.0-44.0 wt.% nickel; (xiv) 44.0-45.0 wt.% nickel; (xlvi) 45.0-46.0 wt.% nickel; (xlvii) > 46.0 wt.% nickel.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0-3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
The extraction cone preferably comprises stainless steel or an alloy comprising: (i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0-4.0 wt.% X; and (v) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
The extraction cone preferably forms an interface between a first or further vacuum chamber of the mass spectrometer and a second or further vacuum chamber of the mass spectrometer. The extraction cone preferably comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
The first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the first or inner conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the first or inner conical or frusto- conical body.
The extraction cone preferably further comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture, wherein the second orifice or annular aperture substantially circumscribes at least part or substantially the whole of the first orifice or circular aperture.
The first coating or surface is preferably provided on: (i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of the second or outer conical or frusto-conical body; and/or (ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of the second or outer conical or frusto-conical body.
The first coating or surface is preferably selected from the group consisting of: (i) aluminium carbide Or AI4C3; (ii) chromium carbide, CrC, Cr23C6, Cr3C, Cr7C3Or Cr3C2; (Ni) copper carbide; (iv) hafnium carbide, HfC or HfCc99; (v) iron carbide, Fe3C, Fe7C3 or Fe2C; (vi) iridium carbide; (vii) manganese carbide, MnC or Mn23C6; (viii) molybdenum carbide, Mo2C or Mo3C2; (ix) nickel carbide or NiC; (x) niobium carbide, NbC, Nb2C, NbC099, or Nb4C3; (xi) osmium carbide; (xii) palladium carbide; (xiii) platinum carbide; (xiv) rhenium carbide; (xv) rhodium carbide or RhC; (xvi) ruthenium carbide; (xvii) scandium carbide or ScC; (xviii) tantalum carbide, TaC, Ta2C, TaC099 or Ta4C3; (xix) titanium carbide or TiC; (xx) tungsten carbide, WC or W2C; (xxi) vanadium carbide, VC, VC097, V4C3; (xxii) yttrium carbide or YC2; (xxiii) zirconium carbide, ZrC or ZrC0.97; and (xxiv) silicon carbide or SiC.
The first coating or surface preferably comprises: (i) a transition metal carbide; (ii) a carbide alloy; or (iii) a mixed metal carbide alloy.
The first coating or surface preferably has either:
(a) a resistivity selected from the group consisting of: (i) < 10"3 Ω-m; (ii) < 10"4 Ω-m; (iii) < 105 Ω-m; (iv) < 10"6 Ω-m; (v) < 10"7 Ω-m; (vi) lO^-W4 Ω-m; (vii) 10^-1O 5 Ω-m; (viii) lO^-IO"6 Ω-m; and (ix) lO^-IO 7 Ω-m; and/or
(b) a Vickers hardness number or Vickers Pyramid Number (HV) selected from the group consisting of: (i) > 1000; (ii) 1000-1100; (iii) 1100-1200; (iv) 1200-1300; (v) 1300- 1400; (vi) 1400-1500; (vii) 1500-1600; (viii) 1600-1700; (ix) 1700-1800; (x) 1800-1900; (xi) 1900-2000; (xii) 2000-2100; (xiii) 2100-2200; (xiv) 2200-2300; (xv) 2300-2400; (xvi) 2400- 2500; (xvii) 2500-2600; (xviii) 2600-2700; (xix) 2700-2800; (xx) 2800-2900; (xxi) 2900- 3000; (xxii) 3000-3100; (xxiii) 3100-3200; (xxiv) 3200-3300; (xv) 3300-3400; (xvi) 3400- 3500; and (xvii) > 3500, wherein the Vickers hardness number or Vickers Pyramid Number is determined at a load of 30, 40, 50, 60 or 70 kg; and/or (c) a Vickers microhardness selected from the group consisting of: (i) > 1000 kg/mm; (ii) 1000-1100 kg/mm; (iii) 1100-1200 kg/mm; (iv) 1200-1300 kg/mm; (v) 1300-1400 kg/mm; (vi) 1400-1500 kg/mm; (vii) 1500-1600 kg/mm; (viii) 1600-1700 kg/mm; (ix) 1700- 1800 kg/mm; (x) 1800-1900 kg/mm; (xi) 1900-2000 kg/mm; (xii) 2000-2100 kg/mm; (xiii) 2100-2200 kg/mm; (xiv) 2200-2300 kg/mm; (xv) 2300-2400 kg/mm; (xvi) 2400-2500 kg/mm; (xvii) 2500-2600 kg/mm; (xviii) 2600-2700 kg/mm; (xix) 2700-2800 kg/mm; (xx) 2800-2900 kg/mm; (xxi) 2900-3000 kg/mm; (xxii) 3000-3100 kg/mm; (xxiii) 3100-3200 kg/mm; (xxiv) 3200-3300 kg/mm; (xv) 3300-3400 kg/mm; (xvi) 3400-3500 kg/mm; and (xvii) > 3500 kg/mm, and/or
(d) a thickness selected from the group consisting of: (i) < 1 μm; (ii) 1-2 μm; (iii) 2-3 μm; (iv) 3-4 μm; (v) 4-5 μm; (vi) 5-6 μm; (vii) 6-7 μm; (viii) 7-8 μm; (ix) 8-9 μm; (x) 9-10 μm; (xi) > 10 μm; and/or
(e) a density selected from the group consisting of: (i) < 3.0 g cm"3; (ii) 3.0-3.5 g cm" 3; (iii) 3.5-4.0 g cm'3; (iv) 4.0-4.5 g cm'3; (v) 4.5-5.0 g cm'3; (vi) 5.0-5.5 g cm"3; (vii) 5.5-6.0 g cm"3; (viii) 6.0-6.5 g cm"3; (ix) 6.5-7.0 g cm"3; (x) 7.0-7.5 g cm"3; (xi) 7.5-8.0 g cm"3; (xii) 8.0- 8.5 g cm'3; (xiii) 8.5-9.0 g cm'3; (xiv) 9.0-9.5 g cm"3; (xv) 9.5-10.0 g cm"3; (xvi) 10.0-10.5 g cm'3; (xvii) 10.5-11.0 g cm'3; (xviii) 11.0-11.5 g cm"3; (xix) 11.5-12.0 g cm"3; (xx) 12.0-12.5 g. cm"3; (xxi) 12.5-13.0 g cm'3; (xxii) 13.0-13.5 g cm"3; (xxiii) 13.5-14.0 g cm'3; (xxiv) 14.0-14.5 g cm'3; (xxv) 14.5-15.0 g cm"3; (xxvi) 15.0-15.5 g cm"3; (xxvii) 15.5-16.0 g cm"3; (xxviii) 16.0- 16.5 g cm"3; (xxix) 16.5-17.0 g cm"3; (xxx) 17.0-17.5 g cm"3; (xxxi) 17.5-18.0 g cm"3; (xxxii) 18.0-18.5 g cm"3; (xxxiii) 18.5-19.0 g cm"3; (xxxiv) 19.0-19.5 g cm"3; (xxxv) 19.5-20.0 g cm"3; and (xxxvi) > 20.0 g cm"3; and/or
(f) a coefficient of friction selected from the group consisting of: (i) < 0.01 ; (ii) 0.01- 0.02; (iii) 0.02-0.03; (iv) 0.03-0.04; (v) 0.04-0.05; (vi) 0.05-0.06; (vii) 0.06-0.07; (viii) 0.07- 0.08; (ix) 0.08-0.09; (x) 0.09-0.10; and (xi) > 0.1.
According to another aspect of the present invention there is provided a method of mass spectrometry comprising: passing ions through a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein the sampling cone and/or the cone-gas cone comprises a first coating or surface provided on at least a portion of the sampling cone and/or the cone-gas cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
According to another aspect of the present invention there is provided a method of mass spectrometry comprising: passing ions through an extraction cone of a mass spectrometer, wherein the extraction cone comprises a first coating or surface provided on at least a portion of the extraction cone, wherein the first coating or surface comprises a metallic carbide coating or surface.
According to another aspect of the present invention there is provided a method of making a sampling cone and/or a cone-gas cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein the first coating or surface comprises a metallic carbide coating or surface. According to another aspect of the present invention there is provided a method of making an extraction cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of an extraction cone of a mass spectrometer, wherein the first coating or surface comprises a metallic carbide coating or surface.
The step of depositing, sputtering or forming the first coating or surface preferably comprises using a method selected from the group consisting of: (i) magnetron sputtering; (ii) closed field unbalanced magnetron sputter ion plating; (iii) electroplating; (iv) thermal spray coating; (v) vapour deposition; (vi) Chemical Vapour Deposition ("CVD"); (vii) combustion torch/flame spraying; (viii) electric arc spraying; (ix) plasma spraying; (x) ion plating; (xi) ion implantation; (xii) sputtering; (xiii) sputter deposition; (xiv) laser surface alloying; (xv) Physical Vapour Deposition ("PVD"); (xvi) plasma-based ion plating; (xvii) gas plasma discharge sputtering; (xviii) laser cladding; (xix) plasma enhanced Chemical Vapour Deposition; (xx) low pressure Chemical Vapour Deposition; (xxi) laser enhanced Chemical Vapour Deposition; (xxii) active reactive evaporation; (xxiii) Pulsed Laser Deposition ("PLD"); (xxiv) RF-sputtering; (xxv) Ion-Beam Sputtering ("IBS"); (xxvi) reactive sputtering; (xxvii) Ion-Assisted Deposition ("IAD"); (xxviii) high target utilisation sputtering; (xxix) High Power Impulse Magnetron Sputtering ("HIPIMS"); and (xxx) DC-sputtering.
According to a preferred embodiment of the present invention a surface coating or a surface modification is preferably used to passivate the surfaces associated with an Atmospheric Pressure lonisation ("API") ion source region and in particular the sampling cone and/or cone-gas cone and/or extraction cone of a mass spectrometer.
The preferred surface coating or surface modification preferably improves the robustness of the sampling cone and/or cone-gas cone and/or extraction cone by reducing surface reactions with ions and/or molecules as ions flow from an atmospheric pressure region to the vacuum chambers of a mass spectrometer. The improved sampling cone and/or cone-gas cone and/or extraction cone preferably has a greater durability, greater resistance to scratching, provides a robust inert surface that reduces the decomposition of contaminants, solvents, and unwanted compounds and is readily cleaned (chemically) without damage or degradation to the inert surface character.
The preferred sampling cone and/or cone-gas cone and/or extraction cone preferably exhibits improved performance characteristics when compared with conventional stainless steel sampling cones, cone-gas cones and extraction cones.
The coated surface preferably advantageously reduces adsorption of material on contact with the surface since if material is deposited onto the surface of the sampling cone, cone-gas cone or extraction cone then it may result in a reduction in signal transmission and may cause an increase in the noise.
Comparative data is presented which shows the differences in intensity and peak area which are observed when using a newly cleaned stainless steel sampling cone/skimmer cone, an aged (or used) stainless steel sampling cone/skimmer cone and an aged (or used) sampling cone/skimmer cone which has been adapted according to the preferred embodiment to have a surface coating. The sampling cone/skimmer cone according to the preferred embodiment maintains its signal transmission while slightly increasing its noise levels (after an extended time period of intermittent use) relative to the cleaned stainless steel sampling cone/skimmer cone. The aged or used stainless steel sampling cone/skimmer cone drops by a greater amount (after an extended time period of intermittent use) and the noise level also increases more significantly.
According to the preferred embodiment a sampling cone, skimmer cone and cone- gas cone which have a surface coating according to the preferred embodiment only require an organic/acid wash whereas a conventional stainless steel sampling cone, congas cone and extraction cone may require abrasive cleaning.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments of the present invention will now be described, by way of example only, and with reference to the accompanying drawings in which:
Fig. 1 shows the initial vacuum stages of a mass spectrometer comprising a sampling cone and a cone-gas cone at the entrance to a first vacuum chamber;
Fig. 2 shows the signal intensity factor difference obtained according to an embodiment of the present invention comparing the intensity of ion signals relating to six compounds obtained using cleaned stainless steel sampling and extraction cones and sampling and extraction cones coated with titanium carbide against an aged stainless steel cone set which was assigned a unity factor;
Fig. 3 shows the signal intensity factor difference for the data shown in Fig. 2;
Fig. 4 shows the peak area factor difference for each of the six compounds with the aged stainless steel cone set being assigned a unity factor; and
Fig. 5 shows a table of the signal to noise factor difference for the six compounds with the aged stainless steel cone set being assigned a unity factor.
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of the present invention will now be described in more detail with reference to Fig. 1. Fig. 1 shows the initial vacuum stages of a mass spectrometer and an Electrospray capillary 1 which forms part of an Electrospray ion source which emits, in use, an ion plume 2. Ions and neutral gas molecules are drawn through a sampling cone 3 into the first vacuum chamber 6 of a mass spectrometer. A cone-gas cone 4 surrounds the sampling cone 3 and a cone gas or curtain gas 5 is preferably supplied to the cone-gas cone 4. Neutral gas molecules continue through the first vacuum chamber 6 which is preferably evacuated by a rough pump 7 such as a rotary pump or scroll pump. The rough pump, rotary pump or scroll pump serves to provide the backing pressure to a second vacuum chamber 9 which is preferably pumped by a fine pump such as a turbomolecular pump or diffusion pump. The term "backing pressure" refers to the pressure in the first vacuum chamber 6. Ions are preferably diverted in an orthogonal direction by an electric field or extraction lens into the second vacuum chamber
9. Ions preferably pass through an extraction cone 8 as they pass from the first vacuum chamber 6 into the second vacuum chamber 9.
An ion guide 11 is preferably provided in the second vacuum chamber 9 which preferably guides ions through the second vacuum chamber 9 and which preferably onwardly transmits ions to subsequent lower pressure vacuum chambers. The second vacuum chamber 9 is preferably pumped by a turbomolecular pump or a diffusion pump
10. Ions exiting the second vacuum chamber 9 preferably pass through a differential pumping aperture 12 into subsequent stages of the mass spectrometer.
According to an embodiment the backing pressure or the pressure in the first vacuum chamber 6 may be maintained, in use, in the range 5 to 9 mbar. The cone-gas cone 4 and the sampling cone 3 of the mass spectrometer may be maintained at a potential of 175 V.
The cone-gas cone 4 and the sampling cone 3 preferably comprise two co-axial cones which are preferably in direct contact with each other and which are preferably maintained at the same potential.
In order to test the performance of the sampling and extraction cones according to the preferred embodiment, a six component mixture of different compounds namely sulphadimethoxine, verapamil, caffeine, acetominophen, chloramphenicol and 17α hydroxyprogesterone were analysed. A liquid chromatography column (for chromatographic separation) with a tandem quadrupole mass spectrometer was used to produce the resulting data.
The six compound mixture was analysed by positive and negative ion Electrospray ionisation (ESI+/ ESI-) using a liquid chromatography column (for chromatographic separation) with a tandem quadrupole mass spectrometer.
Data was acquired using: (i) a conventional stainless steel (SS) sampling and extraction cone; (ii) a sampling and extraction cone coated with titanium carbide (TiC) according to an embodiment of the present invention; and (iii) a cleaned stainless steel (SS) sampling and extraction cone.
The stainless steel and titanium carbide sampling and extraction cones were used for an extended time period to investigate their robustness characteristics.
Figs. 2 and 3 show a comparison of the average intensities observed for each of the six compounds when using a used or aged stainless steel sampling and extraction cone set up, a used or aged sampling and extraction cone coated with titanium carbide (TiC) according to an embodiment of the present invention, and a recently cleaned stainless steel sampling and extraction cone.
Fig. 4 shows a comparison of the average areas observed for each of the six compounds when using a used or aged stainless steel sampling and extraction cone set up, a used or aged sampling and extraction cone set up coated with titanium carbide (TiC) according to an embodiment of the present invention and a recently cleaned stainless steel sampling and extraction cone. From the above data it is apparent that as the stainless steel system ages, the response (sensitivity) and in addition the peak area of the analytes drops between 30-90% (depending upon the compound) with time. By contrast, the coated system according to the preferred embodiment maintains its sensitivity and hence the sample and extraction cone according to the preferred embodiment exhibits improved robustness.
The signal to noise response was also investigated and the data is shown in Fig. 5.
Fig. 5 shows the Signal to Noise factor of an aged or used stainless steel sample and extraction cone, an aged or used TiC sampling and extraction cone according to the preferred embodiment and a cleaned stainless steel sampling and extraction cone.
The results show that the S: N response for the aged stainless steel system is lower than that obtained from both the aged TiC sampling and extraction cone according to an embodiment of the present invention and the cleaned stainless steel sampling and extraction cone set up. This is due to the increased signal intensity obtained from the TiC and cleaned stainless steel sampling and extraction cones and also the lower noise produced from these systems compared to using an aged stainless steel sampling and extraction cone.
In summary, an improvement in robustness was observed using an extraction and sampling cone coated with titanium carbide according to an embodiment of the present invention. The coated surface maintains a higher signal intensity and lower noise response compared to the aged stainless steel environment for all compounds investigated. Cleaning the stainless steel surface regenerated the sample response and lowered the noise response resulting in equivalent results to the aged TiC.
The result of cleaning the TiC surface conferred no further improvement over that of the cleaned stainless steel system.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the scope of the invention as set forth in the accompanying claims.

Claims

Claims
1. A mass spectrometer comprising a sampling cone and/or a cone-gas cone, wherein said sampling cone and/or said cone-gas cone comprise a first coating or surface provided on at least a portion of said sampling cone and/or said cone-gas cone, wherein said first coating or surface comprises a metallic carbide coating or surface.
2. A mass spectrometer as claimed in claim 1, wherein said sampling cone and/or said cone-gas cone is made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ≥ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ≥ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
3. A mass spectrometer as claimed in claim 1 or 2, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-0.01 wt.% carbon; (ii) 0.01-0.02 wt.% carbon; (iii) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06- 0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon.
4. A mass spectrometer as claimed in claim 1, 2 or 3, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03-0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
5. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3- 0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
6. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0- 24.0 wt.% chromium; (xiii) 24.0-25.0 wt.% chromium; (xiv) 25.0-26.0 wt.% chromium; (xv)
26.0-27.0 wt.% chromium; (xvi) 27.0-28.0 wt.% chromium; (xvii) 28.0-29.0 wt.% chromium; (xviii) 29.0-30.0 wt.% chromium; and (xix) > 30.0 wt.% chromium.
7. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% nickel; (ii) 1 /0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (y) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0-11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (XV) 14.0-15.0 wt.% nickel; (xvi) 15.0-16.0 wt.% nickel; (xvii) 16.0-17.0 wt.% nickel; (xviii) 17.0-18.0 wt.% nickel; (xix) 18.0-19.0 wt.% nickel; (xx) 19.0-20.0 wt.% nickel; (xxi) 20.0- 21.0 wt.% nickel; (xxii) 21.0-22.0 wt.% nickel; (xxiii) 22.0-23.0 wt.% nickel; (xxiv) 23.0-24.0 wt.% nickel; (xxv) 24.0-25.0 wt.% nickel; (xxvi) 25.0-26.0 wt.% nickel; (xxvii) 26.0-27.0 wt.% nickel; (xxviii) 27.0-28.0 wt.% nickel; (xxix) 28.0-29.0 wt.% nickel; (xxx) 29.0-30.0 wt.% nickel; (xxxi) 30.0-31.0 wt.% nickel; (xxxii) 31.0-32.0 wt.% nickel; (xxxiii) 32.0-33.0 wt.% nickel; (xxxiv) 33.0-34.0 wt.% nickel; (xxxv) 34.0-35.0 wt.% nickel; (xxxvi) 35.0-36.0 wt.% nickel; (xxxvii) 36.0-37.0 wt.% nickel; (xxxviii) 37.0-38.0 wt.% nickel; (xxxix) 38.0-39.0 wt.% nickel; (xl) 39.0-40.0 wt.% nickel; (xli) 40.0-41.0 wt.% nickel; (xlii) 41.0-42.0 wt.% nickel; (xliii) 42.0-43.0 wt.% nickel; (xliv) 43.0-44.0 wt.% nickel; (xlv) 44.0-45.0 wt.% nickel; (xlvi) 45.0-46.0 wt.% nickel; (xlvii) > 46.0 wt.% nickel.
8. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0-3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
9. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
10. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone comprises stainless steel or an alloy comprising:
(i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0-4.0 wt.% X; and (v) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
11. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone and/or said cone-gas cone forms an interface between an atmospheric pressure ion source and a first vacuum chamber of said mass spectrometer.
12. A mass spectrometer as claimed in any preceding claim, wherein said sampling cone comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
13. A mass spectrometer as claimed in claim 12, wherein said first coating or surface is provided on:
(i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of said first or inner conical or frusto-conical body; and/or
(ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of said first or inner conical or frusto-conical body.
14. A mass spectrometer as claimed in claim 12 or 13, wherein said cone-gas cone comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture through which a cone gas emerges, in use, and wherein said second orifice or annular aperture substantially circumscribes at least part or substantially the whole of said first orifice or circular aperture.
15. A mass spectrometer as claimed in claim 14, wherein said first coating or surface is provided on:
(i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of said second or outer conical or frusto-conical body; and/or
(ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of said second or outer conical or frusto-conical body.
16. A mass spectrometer comprising an extraction cone, wherein said extraction cone comprises a first coating or surface provided on at least a portion of said extraction cone, wherein said first coating or surface comprises a metallic carbide coating or surface.
17. A mass spectrometer as claimed in claim 16, wherein said extraction cone is made from a material selected from the group consisting of: (i) stainless steel; (ii) a steel alloy comprising ≥ 11.5% chromium wt.%; (iii) an austenitic stainless steel; (iv) a ferritic stainless steel; (v) an austenitic-ferritic or duplex steel; (vi) titanium; (vii) a titanium alloy; (viii) a nickel-base alloy; (ix) a nickel-chromium alloy; (x) a nickel-chromium alloy comprising ≥ 50.0% nickel wt.%; and (xi) INCONEL (RTM) 600, 625, 690, 702, 718, 939 or X750.
18. A mass spectrometer as claimed in claim 16 or 17, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-0.01 wt.% carbon; (ii) 0.01-0.02 wt.% carbon; (Ni) 0.02-0.03 wt.% carbon; (iv) 0.03-0.04 wt.% carbon; (v) 0.04-0.05 wt.% carbon; (vi) 0.05-0.06 wt.% carbon; (vii) 0.06- 0.07 wt.% carbon; (viii) 0.07-0.08 wt.% carbon; and (ix) > 0.08 wt.% carbon.
19. A mass spectrometer as claimed in claim 16, 17 or 18, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-0.01 wt.% nitrogen; (ii) 0.01-0.02 wt.% nitrogen; (iii) 0.02-0.03 wt.% nitrogen; (iv) 0.03-0.04 wt.% nitrogen; (v) 0.04-0.05 wt.% nitrogen; (vi) 0.05-0.06 wt.% nitrogen; (vii) 0.06-0.07 wt.% nitrogen; and (viii) > 0.07 wt.% nitrogen.
20. A mass spectrometer as claimed in any of claims 16-19, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-0.1 wt.% nitrogen; (ii) 0.1-0.2 wt.% nitrogen; (iii) 0.2-0.3 wt.% nitrogen; (iv) 0.3- 0.4 wt.% nitrogen; (v) 0.4-0.5 wt.% nitrogen; (vi) 0.5-0.6 wt.% nitrogen; (vii) 0.6-0.7 wt.% nitrogen; and (viii) > 0.7 wt.% nitrogen.
21. A mass spectrometer as claimed in any of claims 16-20, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 12.0-13.0 wt.% chromium; (ii) 13.0-14.0 wt.% chromium; (iii) 14.0-15.0 wt.% chromium; (iv) 15.0-16.0 wt.% chromium; (v) 16.0-17.0 wt.% chromium; (vi) 17.0-18.0 wt.% chromium; (vii) 18.0-19.0 wt.% chromium; (viii) 19.0-20.0 wt.% chromium; (ix) 20.0-21.0 wt.% chromium; (x) 21.0-22.0 wt.% chromium; (xi) 22.0-23.0 wt.% chromium; (xii) 23.0- 24.0 wt.% chromium; (xiii) 24.0-25.0 wt.% chromium; (xiv) 25.0-26.0 wt.% chromium; (xv) 26.0-27.0 wt.% chromium; (xvi) 27.0-28.0 wt.% chromium; (xvii) 28.0-29.0 wt.% chromium; (xviii) 29.0-30.0 wt.% chromium; and (xix) > 30.0 wt.% chromium.
22. A mass spectrometer as claimed in any of claims 16-21 , wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% nickel; (ii) 1.0-2.0 wt.% nickel; (iii) 2.0-3.0 wt.% nickel; (iv) 3.0-4.0 wt.% nickel; (v) 4.0-5.0 wt.% nickel; (vi) 5.0-6.0 wt.% nickel; (vii) 6.0-7.0 wt.% nickel; (viii) 7.0-8.0 wt.% nickel; (ix) 8.0-9.0 wt.% nickel; (x) 9.0-10.0 wt.% nickel; (xi) 10.0-11.0 wt.% nickel; (xii) 11.0-12.0 wt.% nickel; (xiii) 12.0-13.0 wt.% nickel; (xiv) 13.0-14.0 wt.% nickel; (xv) 14.0-15.0 wt.% nickel; (xvi) 15.0-16.0 wt.% nickel; (xvii) 16.0-17.0 wt.% nickel; (xviii) 17.0-18.0 wt.% nickel; (xix) 18.0-19.0 wt.% nickel; (xx) 19.0-20.0 wt.% nickel; (xxi) 20.0- 21.0 wt.% nickel; (xxii) 21.0-22.0 wt.% nickel; (xxiii) 22.0-23.0 wt.% nickel; (xxiv) 23.0-24.0 wt.% nickel; (xxv) 24.0-25.0 wt.% nickel; (xxvi) 25.0-26.0 wt.% nickel; (xxvii) 26.0-27.0 wt.% nickel; (xxviii) 27.0-28.0 wt.% nickel; (xxix) 28.0-29.0 wt.% nickel; (xxx) 29.0-30.0 wt.% nickel; (xxxi) 30.0-31.0 wt.% nickel; (xxxii) 31.0-32.0 wt.% nickel; (xxxiii) 32.0-33.0 wt.% nickel; (xxxiv) 33.0-34.0 wt.% nickel; (xxxv) 34.0-35.0 wt.% nickel; (xxxvi) 35.0-36.0 wt.% nickel; (xxxvii) 36.0-37.0 wt.% nickel; (xxxviii) 37.0-38.0 wt.% nickel; (xxxix) 38.0-39.0 wt.% nickel; (xl) 39.0-40.0 wt.% nickel; (xli) 40.0-41.0 wt.% nickel; (xlii) 41.0-42.0 wt.% nickel; (xliii) 42.0-43.0 wt.% nickel; (xliv) 43.0-44.0 wt.% nickel; (xlv) 44.0-45.0 wt.% nickel; (xlvi) 45.0-46.0 wt.% nickel; (xlvii) > 46.0 wt.% nickel.
23. A mass spectrometer as claimed in any of claims 16-22, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% molybdenum; (ii) 1.0-2.0 wt.% molybdenum; (iii) 2.0-3.0 wt.% molybdenum; (iv) 3.0-4.0 wt.% molybdenum; (v) 4.0-5.0 wt.% molybdenum; (vi) 5.0-6.0 wt.% molybdenum; (vii) 6.0-7.0 wt.% molybdenum; (viii) 7.0-8.0 wt.% molybdenum; and (ix) > 8.0 wt.% molybdenum.
24. A mass spectrometer as claimed in any of claims 16-23, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0-1.0 wt.% copper; (ii) 1.0-2.0 wt.% copper; (iii) 2.0-3.0 wt.% copper; (iv) 3.0-4.0 wt.% copper; and (v) > 4.0 wt.% copper.
25. A mass spectrometer as claimed in any of claims 16-24, wherein said extraction cone comprises stainless steel or an alloy comprising:
(i) 0.01-1.0 wt.% X; (ii) 1.0-2.0 wt.% X; (iii) 2.0-3.0 wt.% X; (iv) 3.0-4.0 wt.% X; and (V) > 4.0 wt.% X; wherein X comprises cobalt and/or tantalum and/or aluminium and/or titanium and/or niobium and/or silicon and/or manganese and/or tungsten and/or phosphorous.
26. A mass spectrometer as claimed in any of claims 16-25, wherein said extraction cone forms an interface between a first or further vacuum chamber of said mass spectrometer and a second or further vacuum chamber of said mass spectrometer.
27. A mass spectrometer as claimed in any of claims 16-26, wherein said extraction cone comprises a first or inner conical or frusto-conical body defining a first orifice or circular aperture through which ions pass in use.
28. A mass spectrometer as claimed in claim 27, wherein said first coating or surface is provided on:
(i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of said first or inner conical or frusto-conical body; and/or
(ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of said first or inner conical or frusto-conical body.
29. A mass spectrometer as claimed in claim 27 or 28, wherein said extraction cone further comprises a second or outer conical or frusto-conical body defining a second orifice or annular aperture, wherein said second orifice or annular aperture substantially circumscribes at least part or substantially the whole of said first orifice or circular aperture.
30. A mass spectrometer as claimed in claim 29, wherein said first coating or surface is provided on:
(i) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an outer surface of said second or outer conical or frusto-conical body; and/or
(ii) at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of an inner surface of said second or outer conical or frusto-conical body.
31. A mass spectrometer as claimed in any preceding claim, wherein said first coating or surface is selected from the group consisting of: (i) aluminium carbide or AI4C3; (ii) chromium carbide, CrC, Cr23C6, Cr3C, Cr7C3Or Cr3C2; (iii) copper carbide; (iv) hafnium carbide, HfC or HfC099; (v) iron carbide, Fe3C, Fe7C3 or Fe2C; (vi) iridium carbide; (vii) manganese carbide, MnC or Mn23C6; (viii) molybdenum carbide, Mo2C or Mo3C2; (ix) nickel carbide or NiC; (x) niobium carbide, NbC, Nb2C, NbC099, or Nb4C3; (xi) osmium carbide; (xii) palladium carbide; (xiii) platinum carbide; (xiv) rhenium carbide; (xv) rhodium carbide or RhC; (xvi) ruthenium carbide; (xvii) scandium carbide or ScC; (xviii) tantalum carbide, TaC, Ta2C, TaC099 or Ta4C3; (xix) titanium carbide or TiC; (xx) tungsten carbide, WC or W2C; (xxi) vanadium carbide, VC, VC097, V4C3; (xxii) yttrium carbide or YC2; (xxiii) zirconium carbide, ZrC or ZrC097; and (xxiv) silicon carbide or SiC.
32. A mass spectrometer as claimed in any preceding claim, wherein said first coating or surface comprises: (i) a transition metal carbide; (ii) a carbide alloy; or (iii) a mixed metal carbide alloy.
33. A mass spectrometer as claimed in any preceding claim, wherein said first coating or surface has either:
(a) a resistivity selected from the group consisting of: (i) < 10"3 Ω-m; (ii) < 10"4 Ω-m; (iii) < 10"5 Ω-m; (iv) < 10"6 Ω-m; (v) < 107 Ω-m; (vi) 10'MO"4 Ω-m; (vii) lO^-IO"5 Ω-m; (viii) lO^-IO"6 Ω-m; and (ix) iσ*-10'7 Ω-m; and/or
(b) a Vickers hardness number or Vickers Pyramid Number (HV) selected from the group consisting of: (i) > 1000; (ii) 1000-1100; (iii) 1100-1200; (iv) 1200-1300; (v) 1300- 1400; (vi) 1400-1500; (vii) 1500-1600; (viii) 1600-1700; (ix) 1700-1800; (x) 1800-1900; (xi) 1900-2000; (xii) 2000-2100; (xiii) 2100-2200; (xiv) 2200-2300; (xv) 2300-2400; (xvi) 2400- 2500; (xvii) 2500-2600; (xviii) 2600-2700; (xix) 2700-2800; (xx) 2800-2900; (xxi) 2900- 3000; (xxii) 3000-3100; (xxiii) 3100-3200; (xxiv) 3200-3300; (xv) 3300-3400; (xvi) 3400- 3500; and (xvii) > 3500, wherein said Vickers hardness number or Vickers Pyramid Number is determined at a load of 30, 40, 50, 60 or 70 kg; and/or
(c) a Vickers microhardness selected from the group consisting of: (i) > 1000 kg/mm; (ii) 1000-1100 kg/mm; (iii) 1100-1200 kg/mm; (iv) 1200-1300 kg/mm; (v) 1300-1400 kg/mm; (vi) 1400-1500 kg/mm; (vii) 1500-1600 kg/mm; (viii) 1600-1700 kg/mm; (ix) 1700- 1800 kg/mm; (x) 1800-1900 kg/mm; (xi) 1900-2000 kg/mm; (xii) 2000-2100 kg/mm; (xiii) 2100-2200 kg/mm; (xiv) 2200-2300 kg/mm; (xv) 2300-2400 kg/mm; (xvi) 2400-2500 kg/mm; (xvii) 2500-2600 kg/mm; (xviii) 2600-2700 kg/mm; (xix) 2700-2800 kg/mm; (xx) 2800-2900 kg/mm; (xxi) 2900-3000 kg/mm; (xxii) 3000-3100 kg/mm; (xxiii) 3100-3200 kg/mm; (xxiv) 3200-3300 kg/mm; (xv) 3300-3400 kg/mm; (xvi) 3400-3500 kg/mm; and (xvii) > 3500 kg/mm, and/or
(d) a thickness selected from the group consisting of: (i) < 1 μm; (ii) 1-2 μm; (iii) 2-3 μm; (iv) 3-4 μm; (v) 4-5 μm; (vi) 5-6 μm; (vii) 6-7 μm; (viii) 7-8 μm; (ix) 8-9 μm; (x) 9-10 μm; (xi) > 10 μm; and/or
(e) a density selected from the group consisting of: (i) < 3.0 g cm"3; (ii) 3.0-3.5 g cm" 3; (iii) 3.5-4.0 g cm"3; (iv) 4.0-4.5 g cm"3; (v) 4.5-5.0 g cm'3; (vi) 5.0-5.5 g cm"3; (vii) 5.5-6.0 g cm'3; (viii) 6.0-6.5 g cm"3; (ix) 6.5-7.0 g cm"3; (x) 7.0-7.5 g cm"3; (xi) 7.5-8.0 g cm"3; (xii) 8.0- 8.5 g cm"3; (xiii) 8.5-9.0 g cm"3; (xiv) 9.0-9.5 g cm"3; (xv) 9.5-10.0 g cm"3; (xvi) 10.0-10.5 g cm"3; (xvii) 10.5-11.0 g cm"3; (xviii) 11.0-11.5 g cm"3; (xix) 11.5-12.0 g cm"3; (xx) 12.0-12.5 g cm"3; (xxi) 12.5-13.0 g cm"3; (xxii) 13.0-13.5 g cm"3; (xxiii) 13.5-14.0 g cm"3; (xxiv) 14.0-14.5 g cm"3; (xxv) 14.5-15.0 g cm"3; (xxvi) 15.0-15.5 g cm"3; (xxvii) 15.5-16.0 g cm"3; (xxviii) 16.0- 16.5 g cm"3; (xxix) 16.5-17.0 g cm"3; (xxx) 17.0-17.5 g cm"3; (xxxi) 17.5-18.0 g cm"3; (xxxii) 18.0-18.5 g cm"3; (xxxiii) 18.5-19.0 g cm"3; (xxxiv) 19.0-19.5 g cm"3; (xxxv) 19.5-20.0 g cm"3; and (xxxvi) > 20.0 g cm"3; and/or
(f) a coefficient of friction selected from the group consisting of: (i) < 0.01; (ii) 0.01- 0.02; (iii) 0.02-0.03; (iv) 0.03-0.04; (v) 0.04-0.05; (vi) 0.05-0.06; (vii) 0.06-0.07; (viii) 0.07- 0.08; (ix) 0.08-0.09; (x) 0.09-0.10; and (xi) > 0.1.
34. A method of mass spectrometry comprising: passing ions through a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein said sampling cone and/or said cone-gas cone comprises a first coating or surface provided on at least a portion of said sampling cone and/or said cone- gas cone, wherein said first coating or surface comprises a metallic carbide coating or surface.
35. A method of mass spectrometry comprising: passing ions through an extraction cone of a mass spectrometer, wherein said extraction cone comprises a first coating or surface provided on at least a portion of said extraction cone, wherein said first coating or surface comprises a metallic carbide coating or surface.
36. A method of making a sampling cone and/or a cone-gas cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of a sampling cone and/or a cone-gas cone of a mass spectrometer, wherein said first coating or surface comprises a metallic carbide coating or surface.
37. A method of making an extraction cone for a mass spectrometer comprising: depositing, sputtering or forming a first coating or surface on at least a portion of an extraction cone of a mass spectrometer, wherein said first coating or surface comprises a metallic carbide coating or surface.
38. A method as claimed in claim 36 or 37, wherein said step of depositing, sputtering or forming said first coating or surface comprises using a method selected from the group consisting of: (i) magnetron sputtering; (ii) closed field unbalanced magnetron sputter ion plating; (iii) electroplating; (iv) thermal spray coating; (v) vapour deposition; (vi) Chemical Vapour Deposition ("CVD"); (vii) combustion torch/flame spraying; (viii) electric arc spraying; (ix) plasma spraying; (x) ion plating; (xi) ion implantation; (xii) sputtering; (xiii) sputter deposition; (xiv) laser surface alloying; (xv) Physical Vapour Deposition ("PVD"); (xvi) plasma-based ion plating; (xvii) gas plasma discharge sputtering; (xviii) laser cladding; (xix) plasma enhanced Chemical Vapour Deposition; (xx) low pressure Chemical Vapour Deposition; (xxi) laser enhanced Chemical Vapour Deposition; (xxii) active reactive evaporation; (xxiii) Pulsed Laser Deposition ("PLD"); (xxiv) RF-sputtering; (xxv) Ion-Beam Sputtering ("IBS"); (xxvi) reactive sputtering; (xxvii) Ion-Assisted Deposition ("IAD"); (xxviii) high target utilisation sputtering; (xxix) High Power Impulse Magnetron Sputtering ("HIPIMS"); and (xxx) DC-sputtering.
39. A method as claimed in any of claims 34-37, wherein said first coating or surface is selected from the group consisting of: (i) aluminium carbide or AI4C3; (ii) chromium carbide, CrC, Cr23C6, Cr3C, Cr7C3 or Cr3C2; (iii) copper carbide; (iv) hafnium carbide, HfC or HfCo.99; (v) iron carbide, Fe3C, Fe7C3 or Fe2C; (vi) iridium carbide; (vii) manganese carbide, MnC or Mn23C6; (viii) molybdenum carbide, Mo2C or Mo3C2; (ix) nickel carbide or NiC; (x) niobium carbide, NbC, Nb2C, NbCo.99, or Nb4C3; (xi) osmium carbide; (xii) palladium carbide; (xiii) platinum carbide; (xiv) rhenium carbide; (xv) rhodium carbide or RhC; (xvi) ruthenium carbide; (xvii) scandium carbide or ScC; (xviii) tantalum carbide, TaC, Ta2C1 TaCo.99 or Ta4C3; (xix) titanium carbide or TiC; (xx) tungsten carbide, WC or W2C; (xxi) vanadium carbide, VC, VC097, V4C3; (xxii) yttrium carbide or YC2; (xxiii) zirconium carbide, ZrC or ZrC097; and (xxiv) silicon carbide or SiC.
PCT/GB2010/000967 2009-05-13 2010-05-13 Surface coating on sampling cone of mass spectrometer WO2010131007A2 (en)

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GB0908249A GB0908249D0 (en) 2009-05-13 2009-05-13 Surface coating on a sampling cone of mass spectrometer
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