U.S. patent number 3,673,405 [Application Number 05/106,576] was granted by the patent office on 1972-06-27 for gas inlet system for a mass spectrometer.
This patent grant is currently assigned to The Bendix Corporation. Invention is credited to Charles J. Moorman, Fred A. Reuter.
United States Patent |
3,673,405 |
Moorman , et al. |
June 27, 1972 |
GAS INLET SYSTEM FOR A MASS SPECTROMETER
Abstract
A mass spectrometer having an improved inlet system which
assures that there is a minimum time lag, generally of the order of
milliseconds, between changes in the composition of a material
being analyzed and the analysis of corresponding changes in the
associated spectra. The inlet system includes a primary leak
directly opposite and closely spaced to a secondary leak leading
into an ionization chamber so that changes in the composition of a
gas leaving the primary leak are more rapidly communicated to the
ionization chamfer for faster analysis by the mass
spectrometer.
Inventors: |
Moorman; Charles J.
(Cincinnati, OH), Reuter; Fred A. (Cincinnati, OH) |
Assignee: |
The Bendix Corporation
(N/A)
|
Family
ID: |
22312169 |
Appl.
No.: |
05/106,576 |
Filed: |
January 14, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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812582 |
Mar 28, 1969 |
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Current U.S.
Class: |
250/288;
250/287 |
Current CPC
Class: |
H01J
49/14 (20130101) |
Current International
Class: |
H01J
49/14 (20060101); H01J 49/10 (20060101); H01j
039/34 () |
Field of
Search: |
;250/41.9G,41.9SB,41.9S,41.9TF ;313/63,230 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"The Encyclopedia of Spectroscopy," Edited B. G. L. Clark,
Published by Reinhold Publishing Corp., New York, 1960, pages
636-639..
|
Primary Examiner: Lindquist; William F.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No.
812,582 filed Mar. 28, 1969 now abandoned.
Claims
Having described the invention, what is claimed is:
1. In combination with a mass spectrometer of the type having an
ionization chamber for ionizing gas, said ionization chamber
including a grid that periodically forces said ionized gas
molecules into an analyzing region wherein said ionized gas
molecules are separated according to their mass-to-charge ratio,
the improvement comprising:
a second chamber having an orifice in one wall, an orifice in
another wall opposite said one wall, and an outlet disposed in said
second chamber between said walls, said outlet adapted to be
connected to a means for evacuating said second chamber, one of
said second chamber walls, having an orifice, forming a common wall
between said second chamber and said ionization chamber;
a tube disposed within said second chamber, said tube having one
end spaced in the range of 13/32 to 1/32 of an inch from the
orifice in said common wall between said ionization chamber and
said second chamber, the other end of said tube extending through
the orifice in the other wall of said second chamber and in fluid
communication with said gas to be ionized so that said gas may
rapidly travel into said ionization chamber from said tube.
2. The combination recited in claim 1 wherein the volume of said
ionization chamber is less than 1 cubic inch.
3. The combination as recited in claim 2 wherein said end of said
tube, spaced from said orifice in said common wall, is located
directly opposite said orifice in said common wall.
4. The combination as recited in claim 3 wherein the thickness of
said common wall between said ionization chamber and said second
chamber is between 0.0001 inch and 0.005 inch.
5. The combination as recited in claim 2 wherein the thickness of
said common wall between said ionization chamber and said second
chamber is between 0.0001 inch and 0.005 inches.
6. The combination as recited in claim 1 wherein the thickness of
said common wall between said ionization chamber and said second
chamber is between 0.0001 inch and 0.005 inch.
7. The combination as recited in claim 1 wherein said end of said
tube, spaced from said orifice in said common wall, is located
directly opposite said orifice in said common wall.
8. An inlet system for a mass spectrometer having an ionization
chamber for ionizing a sample of gas to be analyzed, said
ionization chamber including an aperture for receiving said gas
sample and a grid for periodically accelerating said ionized gas
molecules into an analyzing region wherein said ionized gas
molecules are separated according to their mass-to-charge ratio,
said inlet system comprising:
a second chamber in vacuum-tight relationship with said ionization
chamber with the wall of said ionization chamber having said
aperture therein forming a common wall with said second chamber and
with outlet means adapted to be connected to a means for evacuating
said second chamber and
gas feed means extending through a wall in said second chamber,
said gas feed means having an outlet spaced in the range of 7/32 to
1/32 of an inch from said aperture in said common wall so that gas
samples can be rapidly passed through said feed means, a part of
said second chamber and said aperture in said common wall to said
ionization chamber.
9. The combination as recited in claim 8 wherein the volume of said
ionization chamber is less than 1 cubic inch.
10. The combination as recited in claim 9 wherein the thickness of
said common wall between said ionization chamber and said second
chamber is between 0.0001 inch and 0.005 inch.
11. The combination as recited in claim 8 wherein the thickness of
said common wall between said ionization chamber and said second
chamber is between 0.0001 inch and 0.005 inch.
Description
BACKGROUND OF THE INVENTION
There are many devices and techniques in present use for
introducing a material such as a fluid sample, for example, into
the ionization chamber of a mass spectrometer. Present devices
respond comparatively slowly to changes in the composition of such
fluid and many of such devices have response time which range from
several seconds to several minutes. In applications where speed of
response is not important, these present devices may be acceptable;
however, in applications such as on-stream applications, where the
spectrometer is used to monitor a continuous process, speed of
response is of utmost importance and time-of-flight spectrometers,
with their inherent high speed scanning capability, are of
particular value. Accordingly, it is necessary that the inlet
system for such high speed spectrometers be capable of continuously
providing fresh samples of the spectrometer in a minimum of
time.
SUMMARY OF THE INVENTION
This invention provides an improved mass spectrometer, and a simple
and economical inlet system therefor, which operates with a minimum
time lag generally of the order of milliseconds between changes in
the composition of a material being analyzed and the analysis of
corresponding changes in the associated spectra.
The invention is characterized by a mass spectrometer inlet system
having the outlet of a primary leak located directly opposite and
spaced in the range of 1/32 to 13/32 of an inch from the inlet of a
secondary leak which is located in a wall of the ionization chamber
of a mass spectrometer. Further, the volume of the ionization
chamber with the above spacing should be 1 cubic inch or less.
Other details, uses and advantages of this invention will become
apparent as the following description of the exemplary embodiments
thereof presented in the accompanying drawing proceeds.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing shows a typical prior art device and
present exemplary embodiments of this invention in which:
FIG. l illustrates a typical prior art inlet system for a mass
spectrometer.
FIG. 2 illustrates one exemplary embodiment of this invention.
FIG. 3 illustrates another exemplary embodiment of this
invention.
FIG. 4 is a view taken essentially on the line 4--4 of FIG 3.
DESCRIPTION OF ILLUSTRATED EMBODIMENTS
Reference is now made to FIG. 1 of the drawing which schematically
illustrates a mass spectrometer 10, which may be of any type well
known in the art, having an ionization chamber and drift tube
assembly 11 and a typical prior art inlet system. The inlet system
12 comprises a conduit 13 which contains a fluid, such as gas G,
which is to be analyzed and the gas in conduit 13 may be a moving
stream of such gas. A tube 14 having a small diameter bore 15 is
provided and one end of tube 14 is attached to the conduit 13 with
the opposite end of tube 14 being attached to a tubular housing 16
which defines a chamber 17 of comparatively large volume whereby
gas may be bled from the conduit 13 into the chamber 17 through the
bore 15.
The housing 16 has an inner wall 18 which has an orifice 20
provided therein and the orifice 20 places the chamber 17 in flow
communication with a tube 21 of comparatively large cross-sectional
area which communicates with the ionization and drift tube assembly
11. Another tube 22 is provided and has one end thereof in fluid
flow communication with the chamber 17 and its opposite end is
connected to a suitable vacuum pump 23 which is capable of
providing a high degree of evacuation and in a known manner.
The bore 15 defines what is commonly referred to as a "primary
leak" between the fluid source, i.e., the gas flowing through
conduit 13, and the chamber 17. The orifice 20 defines what is
commonly referred to as a "secondary leak" between the chamber 17
and the ionization chamber and drift tube assembly 11.
With the prior art inlet system 12 a sample of the gas G which is
to be analyzed is drawn from the conduit 13 into the chamber 17
through the primary leak 15. Molecules of the gas G are then passed
by molecular effusion from chamber 17 through the secondary leak 20
into the tube 21 which conveys such molecules to the ionization
chamber and drift tube assembly 11.
The construction and arrangement of inlet system 12 is such that
the outlet of the primary leak or bore 15 is spaced a considerable
distance from, and is generally at right angles to the wall 18
which has the secondary leak or orifice 20 provided therein. With
this construction, it will be seen that an appreciable volume of
gas may accumulate in the chamber 17 which may result in an
appreciable delay between the time gas having a changed composition
enters chamber 17 and the time it moves adjacent the secondary
leak. In addition, the typical prior art inlet system 12 is such
that the ionization chamber of the spectrometer 10 may be spaced
from the secondary leak a distance ranging between roughly a few
centimeters and several feet, whereby a considerable volume may be
provided by the tube 21. Thus, with the typical inlet system 12 it
may take from several seconds to several minutes, as previously
indicated, for new molecules of the gas being analyzed to be moved
from the conduit 13 to the ionization chamber of the spectrometer
10, whereby such inlet system is obviously not satisfactory for use
in applications where samples must be analyzed rapidly.
In the exemplary embodiment of this invention illustrated in FIG. 2
of the drawing a time-of-flight mass spectrometer 24 is illustrated
and comprises an ionization chamber and drift tube assembly 25
which has an ionization chamber 26 provided at one end thereof and
typical ion collector 27 provided at its opposite end. The
spectrometer 24 has an inlet system 30 which enable high speed and
efficient introduction of gas molecules into the ionization chamber
26 which are converted to ions in a known manner by electron
bombardment.
The ions are periodically forced out of the ionization chamber 26
and through the drift tube portion of the assembly 25 toward the
collector 27 by one or more electrical fields established between
appropriate grids provided in the assembly 25. The ions are
propelled toward the collector 27 as a function of their
mass-to-charge ratios whereby they are separated into groups or
bunches with the lightest group reaching the collector 27 first
followed by successively heavier groups. Suitable electrical
circuitry is provided and connected to the collector 27 and may be
made to show a complete mass spectrum of the gas molecules ionized
in the ionization chamber 26. The volume of the ionization chamber
26, i.e., the volume between the diaphragm 37 and the grid closest
to the diaphragm, should be less than one cubic inch and is
preferably 0.03 of a cubic inch (0.005 of a liter).
The spectrometer 24 has its inlet system 30 operatively connected
to a source of fluid or gas which is also designated by the
reference letter G and is to be continuously analyzed and such gas
is provided in a conduit 31 which may be considered a part of such
inlet system. The inlet system includes a tubular housing 33 which
has its inner end fixed in sealed (vacuum-tight) relation to an end
wall 34 of the assembly 25 and the housing 33 has an end plate 36
fixed to its outer end. A think wall in the form of a diaphragm 37
is fixed in a sealed manner to the inner end of tubular wall 33.
The walls 33 and 34 cooperate with the diaphragm 37 to define a
chamber 40 which will be referred to as the second or evacuated
chamber. The second chamber 40 has an outlet 39, communicating with
a suitable pump 41, such as a diffusion pump or molecular pump,
which is capable of providing a high degree of evacuation in said
second chamber.
The diaphragm 37 comprises a substantially planar member which has
opposed surfaces 42 and 43, with surface 42 comprising enclosure
means in the form of one wall for the ionization chamber 26 and the
surface 43 comprising an end wall of the evacuated chamber 40.
Thus, the diaphragm 37 defines a common wall for the evacuated
chamber 40 and the ionization chamber 26.
The inlet system 30 has a capillary tube 44 which extends in sealed
relation through end wall 36. The tube 44 has a passage 45
extending therethrough and the tube 44 is fixed to the conduit 31
so that one end 46 of the passage 45 is in flow communication with
the conduit 31 and the opposite or inner end 47 of the passage 45
is in flow communication with the evacuated chamber 40. In this
embodiment of the invention, the passage 45 defines what is
commonly referred to as the primary leak from the conduit 31 into
the evacuated chamber 40.
The capillary tube 44 is in the form of a tube having the inner end
47 of its passage 45 arranged adjacent to and aligned directly
opposite an orifice 50 which may be provided substantially
centrally in the diaphragm 37. The orifice 50 defines what is
commonly referred to as the secondary leak from the evacuated
chamber 40 into the ionization chamber 26. The inner end 47 of the
tube 44 (primary leak) is arranged directly opposite the orifice 50
(secondary leak) so as to provide a convection in the region of the
secondary leak which removes the remaining portion of a sample once
it is no longer present in the sample of gas leaving the passage
45. It is common in the art of mass spectrometry to have a
differential in pressure between the ionization chamber 26 and the
analyzer chamber. For a discussion of quasi steady-state pressure
characteristics of an inlet system for mass spectrometers see "Mass
Spectroscopy," by M. G. Ingram and R. J. Hayden published by the
National Academy of Sciences-National Research Council, Washington,
D.C. The inner end 47 of the tube 44 is spaced a distance 51 from
the orifice 50. For this type of inlet system the response of the
mass spectrometer to changes in the composition of the sample gas
is optimized if the controlled distance 51 is greater than 1/32 of
an inch but less than 13/32 of an inch. Preferably, the distance 51
is one-sixteenth of any inch.
With the inlet system 30 the gas being analyzed flows through the
primary leak, i.e., passage 45, into the evacuated chamber 40 and
molecules thereof pass through the orifice 50 into the ionization
chamber 26. By providing the diaphragm 37 so that it defines a
common wall between the chamber 40 and the ionization chamber 26,
it will be seen that molecules are introduced directly from chamber
40 into chamber 26 in a minimum of time and with no time delay
being due to travel between the secondary leak and the ionization
chamber as is required in systems proposed heretofore. It will also
be appreciated that by aligning the inner end 47 of the passage 45
so that it is directly opposite the secondary leak or orifice 50
new gas molecules from the conduit 31 are introduced through the
secondary leak and into the ionization chamber 26 with optimum
efficiency.
The diaphragm 37 may be of any suitable thickness and good results
have been obtained with diaphragms having thicknesses generally of
the order of 0.0001 inch and even less. It has also been found that
diaphragms having thicknesses ranging between 0.0001 and 0.005 inch
are comparatively easy to install and use and provide satisfactory
results. Further, the size of the secondary or molecular leak,as it
is often called, is such that is assures effusion of gas molecules
therethrough and such size is determined by well known
techniques.
Thus, it is seen that when primary leak 45 is arranged opposite of
and in the range of 7/32 to 1/32 of an inch from the secondary leak
50 leading into the ionization chamber 26 the spectrometer 24 has a
small response time generally of the order of milliseconds. In
particular, it has been found that by utilizing the construction
and arrangement of components essentially as presented in FIG. 2 of
the drawing, the spectrometer 24 has a response time not exceeding
approximately 30 milliseconds. This response time was verified in
laboratory tests wherein the volume of the ionization chamber 26
was 0.03 of a cubic inch (approximately 0.005 of a liter) and the
pumping speed out of the ionization chamber 26 was one liter per
second making the time required to pump out the ionization region
0.005 of a second. When a gas sample was admitted to the inlet
system 30 the pressure fell to one-tenth of its value (a 90 per
cent change) in about 0.015 of a second. This response time is in
sharp contrast to the comparatively slow response times ranging
between roughly several seconds and several minutes obtained by
present spectrometers using inlet systems of the types proposed
heretofore.
Another exemplary embodiment of this invention is illustrated in
FIGS. 3 and 4 of the drawings. The spectrometer 24 illustrated in
FIGS. 3 and 4 is very similar to the spectrometer 24; therefore,
such spectrometer will be designated generally by the reference
number 24A and parts of the spectrometer 24A which are very similar
to corresponding parts of the spectrometer 24 will be designated by
the same reference numerals as in the spectrometer 24 also followed
by the letter designation A and not described again. Only those
component parts which are substantially different from
corresponding parts of the spectrometer 24 will be designated by
new reference numerals each followed by the letter designation A
and described in detail.
The main difference between the spectrometer 24A and the
spectrometer 24 is in the means utilized in the inlet system 30A to
provide the primary leak from the sample stream or conduit means
31A to the evacuated chamber 40A. In particular, it will be seen
that the conduit means or conduit 31A extends in a sealed
(vacuum-tight) relation through a housing 52A defining the outer
portion of chamber 40A and conduit 31A is arranged adjacent the
common wall means or diaphragm 37A. The conduit 31A has a
thin-walled flat insert disc 53A fixed in sealed vacuum-tight
relation therein and the insert 53A has an aperture 54A provided
therein which defines the primary leak and is arranged directly
opposite the secondary leak or orifice 50A with a distance 51A in
the range of 1/32 to 3/16 of an inch provided therebetween.
Preferably, the distance 51A in this embodiment is one-sixteenth of
an inch. The distance 51A, like the distance 51, may be optimized
within their given ranges depending in part on the characteristics
of the gas G which is to be analyzed and which is contained in the
conduit 31A.
The aperture 54A has an effective area which is controlled so that,
in essence, it provides the equivalent pressure drop that is
provided by the passage 45 in the capillary tube 44, yet it will be
appreciated that the distance that the gas must travel from the
conduit 31A to the secondary leak is substantially reduced whereby
the inlet system 30A and its mass spectrometer 24A will have a more
rapid response time than the spectrometer 24. For a more detailed
discussion of the required pressure differentials, see the
aforementioned article on "Mass Spectroscopy" by Ingram and
Hayden.
The inlet system 30A has another advantage in that it enables the
conduit 31A to extend through the evacuated chamber 40A whereby
that inlet system 30A in addition to providing faster response
times is also more compact.
It should again be emphasized that in both exemplary embodiments of
this invention presented in this specification the secondary or
molecular leak is defined in a common wall between the evacuated
chamber and the ionization chamber and such wall is of minimum
thickness which may be as small as approximately 0.0001 inch. This
arrangement assures that time delays which might be encountered (in
previous inlet systems) by molecules traveling from the secondary
leak to the ionization chamber are substantially eliminated. In
addition, it will be appreciated that with this invention the
cooperating arrangement of the various components of the
spectrometer is such that there is little likelihood that a gas
sample being analyzed will dwell for an appreciable time in the
evacuated chamber before being either rapidly removed therefrom or
molecules thereof effused directly into the ionization chamber.
The pressures at various points in each exemplary inlet system of
this invention may vary within predetermined limits. In an
exemplary operating condition, gas at the source or sample stream
may be at a normal atmospheric pressure. The operation of the
vacuum pump associated with the evacuated chamber is such that the
pressure in such chamber is generally of the order of 100 to 500
microns of mercury and the pressure in the ionization chamber is
generally of the order of 10.sup.-.sup.5 - 10.sup.-.sup.7 mm of
mercury.
Reference has been made throughout this specification to minimum
response time and it should be understood that the response time
referred to is defined as that time increment which elapses from
the time gas first enters the primary leak until the spectrometer
has reached 90 percent of its final output performance.
While present exemplary embodiments of this invention, and methods
of practicing the same, have been illustrated and described, it
will be recognized that this invention may be otherwise variously
embodied and practiced by those skilled in the art.
* * * * *