U.S. patent number 3,845,301 [Application Number 05/252,086] was granted by the patent office on 1974-10-29 for apparatus and methods employing ion analysis apparatus with enhanced gas flow.
This patent grant is currently assigned to Franklin GNO Corporation. Invention is credited to David L. Carroll, Martin J. Cohen, Henry C. Gibson, Roger F. Wernlund.
United States Patent |
3,845,301 |
Wernlund , et al. |
October 29, 1974 |
APPARATUS AND METHODS EMPLOYING ION ANALYSIS APPARATUS WITH
ENHANCED GAS FLOW
Abstract
Plasma chromatograph response time is descreased by improvement
of the gas flow. An ion-molecule reaction region is provided in
tandem with a larger diameter drift region, and a gas outlet is
provided at the junction of the regions. Sample gas flowing through
the ion-molecule reaction region into the drift region is
re-directed by a counter-flow of drift gas through the drift
region, causing both gases to exit through the outlet and reducing
intrusion of the sample gas into the drift region. Diffuse gas flow
is employed in both regions, special structures being provided to
avoid gas jetting.
Inventors: |
Wernlund; Roger F. (Lake Worth,
FL), Carroll; David L. (Lantana, FL), Gibson; Henry
C. (West Palm Beach, FL), Cohen; Martin J. (West Palm
Beach, FL) |
Assignee: |
Franklin GNO Corporation (West
Palm Beach, FL)
|
Family
ID: |
22954540 |
Appl.
No.: |
05/252,086 |
Filed: |
May 10, 1972 |
Current U.S.
Class: |
250/287;
250/286 |
Current CPC
Class: |
G01N
27/622 (20130101) |
Current International
Class: |
G01N
27/64 (20060101); H01J 49/34 (20060101); H01j
039/34 () |
Field of
Search: |
;250/41.9TF,41.9G,286,287 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Borchelt; Archie R.
Assistant Examiner: Anderson; B. C.
Attorney, Agent or Firm: Semmes; Raphael
Claims
1. Ion analysis apparatus and the like comprising an ion-molecule
reaction chamber followed by an ion drift chamber communicating
therewith, means for establishing a drift field along said
chambers, means for introducing a sample gas into said reaction
chamber through an inlet and causing said sample gas to flow
through said reaction chamber toward said drift chamber, means
including an ionizer for forming ions in said reaction chamber by
ion-molecule reactions, outlet means for said gas substantially at
the junction of said chambers and closer to said drift chamber than
said inlet, means for introducing a drift gas into said drift
chamber in counter-flow to the flow of sample gas in said reaction
chamber, and means
2. Apparatus in accordance with claim 1, wherein the
cross-sectional area of the reaction chamber transverse to said
drift field is substantially
3. Apparatus in accordance with claim 1, further comprising means
for
4. Apparatus in accordance with claim 3, wherein said diffusing
means
5. Apparatus in accordance with claim 3, wherein the diffusing
means comprises means for causing the gas to be diffused to change
direction as
6. Apparatus in accordance with claim 3, wherein the diffusing
means comprises means for causing swirling movement of the gas to
be diffused.
7. Apparatus in accordance with claim 6, wherein the means for
causing swirling movement of the gas to be diffused comprises means
for directing that gas substantially tangentially of the chamber
into which it is
8. Apparatus in accordance with claim 1, wherein the reaction
chamber has smaller cross-sectional area transverse to said drift
field than the drift chamber, and the gas outlet is provided
through an end of the drift
9. Apparatus in accordance with claim 1, each of said chambers
being
10. Apparatus in accordance with claim 9, adjacent rings being
insulated from one another and providing controlled gas leakage
paths therebetween.
11. Apparatus in accordance with claim 1, said drift chamber having
a grid
12. Apparatus in accordance with claim 11, said drift chamber
having a further grid thereacross remote from the first-mentioned
grid, said detecting means comprising a signal electrode following
said further grid, said grids being ion gates for selectively
passing ions to said signal
13. Apparatus in accordance with claim 1, said reaction chamber
having smaller cross-sectional area transverse to said drift field
than said drift chamber, and means for diffusing the flow of sample
gas
14. Apparatus in accordance with claim 13, wherein said means for
introducing a drift gas into said drift chamber in counter-flow to
the flow of sample gas in said reaction chamber includes means for
supplying said drift gas at a volumetric flow rate at least several
times the flow
15. Apparatus in accordance with claim 14, further comprising
foraminous means for forming a substantially planar boundary
between said gases
16. Apparatus in accordance with claim 1, wherein said means for
introducing a drift gas into said drift chamber comprises a
chamber
17. Apparatus in accordance with claim 1, further comprising a
housing
18. Apparatus in accordance with claim 17, wherein said gas exhaust
is
19. Apparatus in accordance with claim 18, said housing having a
baffle therein surrounding the end of said reaction chamber remote
from said
20. Apparatus in accordance with claim 1, wherein said drift
chamber has an electrode therein with an aperture therethrough for
the passage of ions to
21. Apparatus in accordance with claim 1, said detecting means
comprising a foraminous electrode in said drift chamber, and said
means for introducing a drift gas into said drift chamber including
means for passing said drift
22. Apparatus in accordance with claim 1, further comprising means
for maintaining the pressure in said chambers at a level such that
the length of the mean free path of ions therein is substantially
less than the
23. Apparatus in accordance with claim 1, wherein said chambers are
defined in part by electric field guard rings, said gas outlet
being provided
24. A method of ion analysis, which comprises providing
communicating ion-molecule reaction and drift chambers in tandem,
with the drift chamber having larger cross-sectional area than the
reaction chamber and with a gas outlet from the region of the
junction of said chambers, causing a sample gas to flow from an
inlet to said reaction chamber and along said reaction chamber in a
direction toward said drift chamber and said junction, producing
product ions from said sample gas by ion-molecule reactions in said
reaction chamber, applying a drift field along said chambers in the
direction of said sample gas flow and causing said ions to pass
from said reaction chamber and then through said drift chamber,
detecting at least a portion of the ions in said drift chamber, and
causing a drift gas to flow through said drift chamber toward said
junction in counter-flow to the flow of sample gas and at a
sufficient volumetric flow rate to re-direct said sample gas
through the gas outlet.
25. A method in accordance with claim 24, further comprising
maintaining the pressure in said chambers at a level such that the
mean free path of
26. A method in accordance with claim 24, further comprising
segregating the ions in said drift chamber in accordance with their
drift velocity.
27. A method in accordance with claim 24, wherein the pressure in
said drift chamber is maintained high enough to cause said ions to
reach substantially constant statistical drift velocity dependent
upon ion mass.
28. A method in accordance with claim 24, further comprising
causing said sample gas to flow diffusely through said reaction
chamber and into said
29. A method in accordance with claim 28, further comprising
causing said
30. A method in accordance with claim 24, wherein said sample gas
is
31. A method in accordance with claim 24, wherein said drift gas
is
32. A method in accordance with claim 24, wherein at least one of
said
33. Ion analysis apparatus comprising an ion-molecule reaction
chamber communicating with an ion drift chamber, means for
producing ions by ion-molecule reactions in said reaction chamber,
means for establishing a drift field along said chambers for
causing ions to move along said reaction chamber and into and along
said drift chamber, means for segregating ions in said drift
chamber in accordance with their drift velocity, means for
detecting at least some of the segregated ions, the cross-sectional
area of said reaction chamber transverse to said drift field being
substantially less than the cross-sectional area of said drift
chamber, and means for introducing a sample gas into said reaction
chamber
34. Apparatus in accordance with claim 33, further comprising means
for causing said gases to flow diffusely in said chambers,
respectively,
35. Apparatus in accordance with claim 33, said chambers being
defined at
36. Apparatus in accordance with claim 33, further comprising means
for maintaining the pressure in said chambers at a level such that
the mean free path of ions in said chambers is short compared to
the dimensions of said chambers and such that said ions reach
substantially constant
37. Ion analysis apparatus comprising an ion-molecule reaction
chamber communicating with an ion drift chamber, means for
introducing a sample gas into said reaction chamber, means for
introducing a drift gas into said drift chamber, means for
producing ions by ion-molecule reactions in said reaction chamber,
means for establishing a drift field along said chambers for
causing ions to drift along said reaction chamber and into and
along said drift chamber, means for segregating ions in said drift
chamber in accordance with their drift velocity, means for
detecting at least some of the segregated ions, means for causing
the gases to flow in said chambers, respectively, in counter-flow
and means including a gas diffusion screen for causing at least
said sample gas to flow diffusely through said reaction chamber and
preventing said sample gas from jetting
38. Apparatus in accordance with claim 37, further comprising means
providing a gas outlet adjacent to the junction of said chambers
and means for supplying said drift gas to said drift gas
introducing means at a volumetric flow rate sufficient to prevent
substantial intrusion of said
39. Apparatus in accordance with claim 38, further comprising means
for forming a substantially planar boundary between said gases
adjacent to
40. Apparatus in accordance with claim 39, the last-mentioned
means
41. Ion analysis apparatus comprising a chamber, means for
introducing a sample gas into said chamber, means for producing
ions in said chamber from said sample gas, means for establishing
an electric drift field along said chamber, means for detecting at
least some of the ions after the ions have moved along said
chamber, and a series of guard rings spaced along said chamber for
maintaining the drift field along said chamber, said guard rings
having circuitous junctions for controlling the leakage of gas
42. Ion analysis apparatus and the like comprising an envelope
having a pair of electrodes spaced apart therein, means for
introducing a sample gas into said envelope, means including an
ionizer adjacent to one of said electrodes for forming ions of said
sample by ion-molecule reactions, means for establishing a drift
field between said electrodes and causing said ions to drift toward
the other of said electrodes, shutter grid means between said
electrodes for segregating ions in the space between said
electrodes in accordance with their drift velocity, means adjacent
to said other electrode for detecting at least some of the
segregated ions, a plurality of guard rings arranged in series
between said electrodes and spaced from said envelope, and means
including an annular shield extending between one of said rings and
said envelope for shielding the detector means from said shutter
grids and for introducing a drift gas into said envelope in
counter-flow to said sample gas.
Description
BACKGROUND OF THE INVENTION
This invention relates to apparatus and methods for performing
measurements upon gaseous samples and is more particularly
concerned with improving the response time of trace gas measurement
apparatus and methods.
The present invention has special applicability to the field of
"Plasma Chromatography," which is described, for example, in U.S.
Pat. No. 3,626,180, granted Dec. 7, 1971, and assigned to the same
assignee as the present application. It will be apparent to those
skilled in the art, however, that certain aspects of the invention
have applicability to other fields as well.
Plasma Chromatography involves the formation of primary or reactant
ions and the reaction of such ions with molecules of trace
substances to form secondary or product ions, which may be
concentrated, separated, detected, and measured by virtue of the
difference of velocity or mobility of the ions in an electric
field. The primary ions may be produced by subjecting the molecules
of a suitable host gas, such as air, to ionizing radiation, the
ions being subjected to an electric drift field which causes them
to move in a predetermined direction through a reaction space into
which the sample or trace gas is introduced. The resultant
ion-molecule reactions produce the product ions. Plasma
Chromatography is performed at a pressure, preferably atmospheric,
such that the length of the mean free path of the ions is very
short compared to the dimensions of reaction and drift regions,
providing efficient generation of product ions and permitting the
ions to reach substantially constant, mass-dependent, statistical
drift velocity, so that they may be readily segregated for
detection as separate ion species.
As set forth in the aforesaid prior patent, it has been proposed to
employ a non-reactive or inert drift gas in order to reduce or
quench ion-molecule reactions in the drift region. The utilization
of such a drift gas reduces interfering ion species and enhances
resolution of the desired ion species in the Plasma
Chromatogram.
Despite the employment of a non-reactive drift gas in the drift
region (with the attendant improvement referred to above), the
sample gas intrudes into the drift region to an undesired extent,
reducing the effectiveness of the drift gas and increasing the time
required to clear the sample and reaction products from the Plasma
Chromatograph substantially beyond that which would be required if
the drift region were maintained largely free of sample gas.
BRIEF DESCRIPTION OF THE INVENTION
It is accordingly a principal object of the present invention to
provide improved ion analysis apparatus and methods.
Another object of the invention is to provide improved gas flow in
a Plasma Chromatograph or the like.
A further object of the invention is to provide an improved Plasma
Chromatograph structure.
Briefly stated, the present invention employs an ion-molecule
reaction region in tandem with a drift region of larger diameter.
At the junction of the regions, a gas outlet is provided. The
regions are defined by two series of guard rings, which maintain
uniformity of an electric field established between electrodes at
the remote ends of the reaction and drift regions. A sample gas is
admitted to the reaction region adjacent to an ionizer and is
caused to flow diffusely toward the drift region. A drift gas is
similarly admitted to the drift region and is caused to flow
diffusely toward the reaction region. Both gases pass through the
outlet, with the flow of drift gas being sufficient to re-direct
the sample gas and to prevent significant intrusion of the sample
gas into the drift region. An ion gate shutter grid, located in the
drift region adjacent to the gas outlet, assists in this respect.
This grid is employed in conjunction with a second ion gate shutter
grid in the drift region to pass selected ion species to an ion
detector.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further described in conjunction with the
accompanying drawings, which illustrate preferred and exemplary
embodiments, and wherein:
FIG. 1 is a diagrammatic longitudinal sectional view of one form of
the invention;
FIG. 1A is a fragmentary longitudinal sectional view of a detail of
the invention;
FIG. 2 is a fragmentary diagrammatic longitudinal sectional view of
a modification;
FIG. 3 is a similar view of another modification;
FIG. 4 is a similar view of another modification; and
FIG. 5 is a diagrammatic transverse sectional view of a further
modification.
Referring to the drawings, and initially to FIG. 1 thereof,
reference numberal 10 designates a Plasma Chromatograph of the type
generally disclosed in the aforesaid prior patent. In the present
invention, the ion-molecule reaction region 12 and the drift region
14, arranged in tandem, are, in effect, communicating chambers
defined in part by two series of guard rings 16 and 18, the guard
rings of the latter series being of larger diameter, so that the
drift chamber has larger cross-sectional area transverse to a drift
field than the reaction chamber. A unidirectional electric drift
field is established between a repeller electrode 20 and a further
electrode 21, at the remote ends of the chambers, respectively. The
drift field has a polarity dependent upon the polarity of the ions
to be detected. An ionizer, such as a tritium or nickel-63 film 24,
is provided upon one of the guard rings adjacent to electrode 20.
The guard rings may be interconnected by a series of resistors (not
shown) to maintain the uniformity of the electric field between
electrodes 20 and 21.
The drift chamber 14 is provided with a pair of ion gates, such as
shutter grids 26 and 28, adjacent to opposite ends thereof. As set
forth in the aforesaid prior patent, each grid is a dual grid
formed of interdigitated coplanar grid sections, with the sections
normally being maintained at equal and opposite potentials with
respect to a grid average potential established by the D.C. supply
connected to electrodes 20 and 21 and guard rings 16 and 18. Each
shutter grid is opened, for the passage of ions therethrough, by
driving the grid sections thereof to the grid average potential. A
further grid, a unipotential shield grid 30, may be provided
between the second shutter grid 28 and a signal electrode 22. The
signal electrode 22 is a fine mesh of about 200/in. The grids 26,
28 and 30 have a porosity of about 50/in. Connections to the grids
and other electrodes may be made by leads which pass through
insulators 32 in the wall of a metal housing or case 34 which
surrounds chambers 12 and 14. Gas exhausts 36 are provided at the
reaction chamber end of the housing.
Sample gas is introduced into the reaction chamber by an inlet pipe
38 extending axially of the chambers. The inlet pipe passes into
the repeller electrode structure 20 and has a mouth facing a wall
40. The entering gas is thus re-directed transversely and then
passes through diffusion screens 42 and past the ionizer 24. By
this arrangement, the sample gas is prevented from jetting into and
through the reaction region and is caused to flow diffusely from
inlet 38 through reaction chamber 12 in the direction of the drift
field and toward the junction of the reaction region and the drift
region.
A non-reactive drift gas, such as nitrogen or dry air, is
introduced into the drift chamber by an inlet pipe 44 extending
axially of the chambers. The drift gas is re-directed transversely
by a wall 46 spaced from the mouth of the inlet pipe 44 and then
passes through diffusion screens 48 and the foraminous signal
electrode 22, shield grid 30 and second shutter grid 28. By this
arrangement, the flow of drift gas in the drift chamber is
diffused, as distinguished from a jet, and is counter to the flow
of sample gas in the reaction region.
The bending and screening of the gas flow from the inlets 38 and 44
absorbs and decreases linear gas flow velocity and smooths the flow
of gas to a substantially uniform one across the entire diameter of
the chambers 12 and 14.
It is necessary that adjacent guard rings be insulated from one
another in order to perform their electrical functions. This is
achieved by the use of air gaps defined by ball insulators 18' (in
appropriate depressions) between successive rings, as shown in FIG.
1A. The ring junctions in the present invention are preferably
re-entrant or dove-tailed to provide circuitous paths for gas, as
shown in FIG. 1A, to reduce the gas flow between the rings. Thus,
although there is some leakage between rings, most of the gas in
the reaction chamber 12 and the drift chamber 14 flows the full
length of the chambers. The grids may be mounted in rings similar
to the guard rings and the entire stack of electrodes, guard rings
and grids (with the interposition of ball insulators) may be
clamped between end plates (not shown) by means of adjustable
longitudinal screw-rods, in a well-known manner.
At the junction of the chambers, a gas outlet 50 is provided. This
outlet may be constituted by a plurality of openings or by screens
or screen sections in a ventilating guard ring which serves as the
end ring of each series and is closer to the drift chamber 14 than
the inlet 38. The volumetric flow of drift gas is made
substantially higher than the flow of sample gas, preferably from 3
to 10 times higher, so that the drift gas effectively re-directs
the sample gas at the chamber junction and so that both gases exit
through the outlet 50. The first shutter grid 26, which is adjacent
to the outlet, assists in re-directing the sample gas and
preventing substantial intrusion of the sample gas into the drift
region, the net effect being the formation of a planar gas
intersection or boundary. A cylindrical baffle 52, which surrounds
the inlet end of the chamber 12, and the provision of the gas
exhausts 36 at the locations shown, tend to prevent pockets of gas
from remaining as a result of earlier sample flow and to prevent
recirculation of output gas into the ion-molecule reaction region.
The slight gas leakage between the guard rings assists in
ventilating the case 34.
The electrical operation of the Plasma Chromatograph of the present
invention is substantially the same as that set forth in the
aforesaid prior patent. Product ion species of different mobility
are efficiently produced in the reaction chamber 12, at the
preferred atmospheric operating pressure, and reach substantially
constant statistical drift velocity dependent upon ion mass. The
ion species are sorted by successively opening the grids 26 and 28,
selected ion species producing signals at electrode 22, which are
detected in the usual manner.
FIG. 2 illustrates a modification of the invention which may be
utilized when it is desired to employ the Plasma Chromatograph in
conjunction with a mass spectrometer, as set forth, for example, in
U.S. Pat. No. 3,621,240, granted Nov. 16, 1971, and assigned to the
same assignee as the present invention. In this embodiment, the
left portion of which is identical to FIG. 1, a signal electrode
22' is provided with a central aperture 54 aligned with an aperture
56 in a wall 58 separating the Plasma Chromatograph from the mass
spectrometer 59, which operates under high vacuum conditions. These
apertures pass an ion beam to the mass spectrometer. Wall 58 may
constitute the electrode of polarity opposite to that of the
repeller electrode. A circular baffle 60 (at case potential)
connected to one of the guard rings 18 by an insulating washer 62
(of mica or quartz, for example) provides an annular chamber 64
surrounding the adjacent end of the drift chamber 14 and into which
the drift gas may be introduced by means of an inlet pipe 44'. The
drift gas enters the drift chamber through openings in an outer
perforated portion 66 of electrode 22'. Baffle 60 also serves as an
electrical shield between the pulsed grid circuits (shutter grids)
and the electrometer circuitry which may be connected to electrode
22' for providing an output directly from the Plasma
Chromatograph.
FIG. 3 illustrates an embodiment like FIG. 1, except that
additional mesh baffles 68 are provided to assist in smoothing the
drift gas flow.
FIG. 4 illustrates a modification of the sample gas outlet. In this
instance, the sample gas enters the repeller electrode structure 20
transversely, as shown at 38'. As illustrated in FIG. 5, at 38",
the inlet pipe may be oriented tangentially to create a swirling
motion of the sample gas, which assists in producing a more
moderate, less jet-like gas flow. Similar orientation of the drift
gas inlet 44' in FIG. 2 may be utilized for the same purpose.
In a typical apparatus of the invention, the inner diameter of the
reaction region may be about 1/2 inch and that of the drift region
11/2 inches. Sample gas flow may range between 50-300 cc/min and
drift gas flow between 300-1000 cc/min (the ratio of drift gas to
sample gas flow preferably being at least three, as stated
previously). The sample gas may be constituted by a sample in an
inert carrier, for example.
The improved gas flow of the invention provides much faster
reaction region clearing, much faster response, high sensitivity,
predictable reaction region performance, and better resolution.
Sample and drift gas preheaters may be employed to obtain better
uniformity of gas temperature in the ion drift region, for further
improvement.
While preferred embodiments of the invention have been shown and
described, it will be apparent to those skilled in the art that
changes can be made in these embodiments without departing from the
principles and spirit of the invention, the scope of which is
defined in the appended claims.
* * * * *