U.S. patent number 3,901,601 [Application Number 05/435,338] was granted by the patent office on 1975-08-26 for chopper arrangement for atomic absorption spectrophotometer.
This patent grant is currently assigned to Bodenseewerk Perkin-Elmer & Co., G.m.b.H.. Invention is credited to Werner K. Lahmann.
United States Patent |
3,901,601 |
Lahmann |
August 26, 1975 |
Chopper arrangement for atomic absorption spectrophotometer
Abstract
An atomic absorption spectrophotometer incorporating
discrimination against "background" absorption, i.e., absorption
not caused by the resonant line absorption by the element being
measured. The device includes a resonant line emitting source
(e.g., a hollow cathode lamp) and a continuous spectrum light
source (e.g., a deuterium lamp), a monochromator and a detector
system. The improvement comprises a specific chopper arrangement
which sequentially causes: (a) the resonant line light from the
hollow cathode lamp to go to the sample path, (b) this light to go
to the reference path, (c) the continuous spectrum light from the
deuterium lamp to go to the reference path, and finally (d) the
continuous spectrum light to go to the sample path. By comparing
the light intensities during intervals (c) and (d) the effect of
the background absorption can be determined and compensated for so
as to determine the relationship between (a) and (b) free of the
effect of such background absorption. The specific improvement
includes a sector mirror and disk-shaped mask which are conjointly
rotated in the angularly intersecting paths of the radiation from
the cathode lamp and the deuterium lamp.
Inventors: |
Lahmann; Werner K. (Uberlingen,
DT) |
Assignee: |
Bodenseewerk Perkin-Elmer &
Co., G.m.b.H. (Uberlingen, Bodensee, DT)
|
Family
ID: |
5869907 |
Appl.
No.: |
05/435,338 |
Filed: |
January 21, 1974 |
Foreign Application Priority Data
|
|
|
|
|
Jan 25, 1973 [DT] |
|
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2303533 |
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Current U.S.
Class: |
356/325;
359/226.1; 359/235; 250/233 |
Current CPC
Class: |
G01J
1/36 (20130101); G01N 21/3103 (20130101) |
Current International
Class: |
G01J
1/10 (20060101); G01J 1/36 (20060101); G01N
21/31 (20060101); G01j 003/42 () |
Field of
Search: |
;250/233
;350/266,273,274,285 ;356/87,93-95,97 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Woodriff et al., Applied Spectroscopy, Vol. 24, No. 5,
September/October 1970, pages 530-533. .
Woodriff et al., Applied Spectroscopy, Vol. 27, No. 3, May/June
1973, pages 181-185. .
Dick et al., Applied Spectroscopy, Vol. 27, No. 6,
November/December 1973, pages 476-470..
|
Primary Examiner: Wibert; Ronald L.
Assistant Examiner: Evans; F. L.
Attorney, Agent or Firm: Giarratana; S. A. Masselle; F.
L.
Claims
What is claimed is:
1. In a double-beam atomic absorption spectrophotometer having a
sample beam path passing through an atomized sample substance and a
reference beam path, including a line-emitting first light source
which emits a resonance line of an element of interest desired to
be measured and a second light source emitting a continuous
spectrum, a monochromator for selecting a limited spectral range
containing the said resonance line from the entire continuous
spectrum, a detector impinged upon by the sample and reference
beams of light, and a signal analyzer circuit connected to generate
an output signal from the detector corrected with respect to the
background absorption,
a chopper arrangement by which, in a predetermined cyclical
sequence of four successive intervals, light from the line emitting
first light source is directed to the sample and reference paths
and light from the continuous spectrum second light source is
similarly directed to the sample and reference paths, said chopper
arrangement comprising:
a sector mirror and an opaque mask rotating coaxially and
conjointly therewith;
said sector mirror having two angularlyspaced reflecting sectors,
arranged respectively on its opposite faces and, angularly
interposed between said sectors, a pair of light-transmitting
cutout portions;
said mask comprising two partially cutout portions, including an
arcuate aperture and a cutout portion of different radii, extending
across a respective one of the transmitting cutout portions of the
sector mirror, and a completely open sector in aligned position
with the reflecting sector on the side facing the mask;
and means for causing the beams of light from the first and the
second light source to impinge obliquely upon said second mirror
substantially reflectingly symmetrically to the sector mirror in
the range of the reflecting sectors, so that one of said partially
cutout portions of the mask passes one of the beams of light
impinging thereon and the other passes the other beam of light to
the sample path and the reference path during intervals when
transmitting cutout portions of said sector mirror allow the beams
of light of pass through said sector mirror.
2. An atomic absorption spectrophotometer as claimed in the claim
1, in which:
said reflecting sectors (32,34) of said sector mirror are
diametrically opposite each other with respect to the axis of
rotation (28) and said light-transmitting cutout portions (36,38)
are interposed therebetween.
3. An atomic absorption spectrophotometer as claimed in claim 2, in
which:
the reflecting sectors of the sector mirror are symmetrically
disposed with respect to a first diametral line normal to said axis
of rotation and the light-transmitting cutout portions are
symmetrically disposed with respect to a second diametral line
normal to the first diametral line and to the axis of rotation.
4. An atomic absorption spectrophotometer as claimed in the claim
2, in which:
both of the beam axes of the two beams of light (10,20) impinging
upon the sector mirror from the first and second light source,
respectively, are in a plane containing the axis of rotation (28)
of the chopper arrangement (18) and are inclined towards this axis
of rotation (28) with respect to the surface normal.
5. An atomic absorption spectrophotometer as claimed in the claim
4, in which:
said arcuate shaped aperture (44) of said mask (30) extends
angulary across the one cutout portion (36) of the sector mirror
(26) in the radial range of the point of intersection of the beam
of light (20) on the side of the mask though the plane of the mask
(30);
a cutout portion (50) at the periphery of said mask is in the
radial range of the point of intersection of the beam of light (20)
reflected on the reflecting sector (34) on the side of the mask
though the plane of the mask (30) which angularly extends across
the other cutout portion (38) of the sector mirror (26), and
said completely open portion (51) extends radially across both
points of intersection and is angularly aligned with the mirror
(34) on the sector on the side of the mask.
6. An atomic absorption spectrophotometer as claimed in the claim
5, in which:
at the edges of the reflecting sectors (32,34) there are provided
absorbing sectors (40,42) for generating a dark signal each.
7. An atomic absorption spectrophotometer as claimed in the claim
2, in which:
said sector mirror (26) comprises a disk-shaped carrier of
light-transmitting material on which the reflecting sectors (32,34)
are applied as bilaterally reflecting layers, and that these
reflecting layers are covered on one respective side each by an
absorbing layer.
8. An atomic absorption spectrophotometer as claimed in the claim
7, in which
said mask comprises a thin circular disk.
Description
FIELD OF THE INVENTION
This invention relates to an atomic absorption spectrophotometer in
the form of a "double-beam" instrument having a sample beam path
passing through an atomized sample substance and a reference beam
path. More particularly, the invention relates to double-beam
instruments which include a light source for emitting a resonance
line of the desired to be measured element of interest; a second
light source emitting a continuous spectrum; and a chopper
arrangement by which in predetermined cyclical sequence (in four
successive intervals) light from the line-emitting first light
source is directed alternately to the sample and reference paths
and during other intervals light from the continuous spectrum light
source is alternately directed to the sample and reference
paths.
PRIOR ART
In atomic absorption spectrometry a sample substance is brought
into a substantially atomic state, for instance, by spraying it
into a flame. The sample substance thus brought into an atomic
state has passed therethrough a sample light beam which originates
from a line-emitting light source, including a resonance line of an
element in the sample substance desired to be measured. A narrow
band of wavelengths including the resonance line is selectively
passed by means of a monochromator and caused to impinge upon a
detector. The desired (to be measured) element in the sample
substance specifically absorbs the resonance line which
theoretically at least is not absorbed by the other elements in the
sample substance. Thus, the absorption degree of the sample beam of
light is representative of the amount of the wanted element in the
sample substance.
In order to take into account changes in the lamp brightness and
changes in the sensitivity of the detector, a double-beam
instrument is generally utilized; in such an instrument the beam of
light originating from the spectral light source is alternately
directed across a sample path which passes through the atomized
sample substance and across a reference path which by-passes the
atomized sample. The sample and reference beams are then directed
(alternately) onto a common detector. The detector signals are
domodulated and an output signal is generated which is a function
of the relation of the signal proportions originating from the
sample and reference light beams. See, for example, Kahn and
Slavin, "An Atomic Absorption Spectrophotometer" in Applied Optics,
1963, pages 931-936).
The assumption that the resonance line of the desired element is
absorbed or attenuated only by that element, so that the intensity
of the sample beam in relation to the intensity of the reference
beam is an accurate and definite measure of the amount of the
element of interest, does not necessarily apply in practice. A
"background absorption" often occurs which can be caused by
molecular absorption, absorption due to the solvent of the sample
solution or by scattering, caresed for instance, by salt crystals.
This background absorption may falsify the measured value obtained
by the atomic absorption spectrophotometer to a considerable
extent.
It is known in the prior art to compensate for this background
absorption (DT-OS 1,911,048 and DT-OS 2,207,298). Such compensation
is based on the fact that the background absorption is a quantity
which changes relatively slowly with the wavelength in contrast to
the absorption (at a single wavelength) of the resonance line by
the element being measured. Therefore, the background absorption
can be measured by using light from a source supplying a continuous
spectrum. The monochromator selects a narrow range of wavelengths
of the continuous spectrum which contains the resonance line of the
desired element. This wavelength range is also subjected to the
background absorption which can be considered substantially
constant across the whole range. The absorption to which this
continuous radiation is subjected in the small range of the narrow
resonance line by the atoms of the element of interest can be
practically neglected as compared with the total absorption in the
substantially wider wavelength range. By a comparison of the sample
beam intensity which results for the selected wavelength range of
the continuous spectrum with the intensity of the beam in the
reference path, the background absorption can be determined. This
background absorption can then be compensated for or mathematically
utilized during the signal analysis.
Therefore, prior art background absorption compensating atomic
absorption spectrophotometers have two light sources, that is, a
line-emitting light source (which is conventionally constituted by
a hollow cathode lamp), and a light source supplying a continuous
spectrum, (for instance a deuterium lamp). For double beam
background compensation, a chopper arrangement must be provided so
that in a fixed sequence of four successive intervals the light of
each of the light sources is directed on the one hand along the
sample path of rays and on the other hand along the reference path
of rays.
In a prior art system (DT-OS 1,911,048 corresponding to U.S. patent
application Ser. No. 710,802 filed Mar. 6, 1968 and now abandoned),
a chopper arrangement comprises a rotating sector mirror by which
the beams of light originating from a hollow cathode lamp and a
deuteriumgas discharge lamp are alternately directed into the
sample path. However the instrument, although originally a
double-beam spectrophotometer, is used only as a single beam
spectrophotometer in this background absorption compensation mode.
In particular an auxiliary shutter blocks the reference path
continuously when the two light sources and rotating sector mirror
chopper are utilized.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a mechanically simple
chopper arrangement for atomic absorption spectrophotometers of the
double-beam type for providing double-beam background absorption
compensation. In particular the chopper arrangement passes
radiation from each of the spectral line source and the continuous
spectrum source to each of the sample and reference paths in four
separate time intervals.
It is another object of this invention to so devise an arrangement
of this type wherein the light sources are arranged in a readily
accessible manner and are imaged by substantially similar paths of
rays so that in the sample and reference beam paths substantially
geometrically identical beams from the two light sources are
alternatingly obtained.
According to the invention this object is attained by a chopper
arrangement which includes a sector mirror as well as a mask
rotating coaxially and synchronously therewith. The sector mirror
has two reflecting sectors arranged on its opposite sides and has
two light-transmitting cutout portions. The mask has two partially
masking portions consisting respectively of an arcuate aperture and
a cutout portion, each of different radii and each extending across
one transmitting cutout portion of the sector mirror. In addition
the mask has an open sector in the range of the reflecting sector
which faces the mask. The beams of light from the first and the
second light sources obliquely impinge in a substantially
symmetrical way upon the sector mirror in the range of the
reflecting sectors; one of the partially transmitting portions of
the mask (e.g. its arcuate aperture) and its other partially
transmitting portion (e.g., the cutout portion) transmit,
respectively, the sample and the reference beams.
Then, on the one hand, from the "front" reflecting sector of the
sector mirror the light from the one light source, for instance,
the line-emitting hollow cathode lamp is reflected for instance
into the sample path. In another position the light from the hollow
cathode lamp is transmitted through a transmitting portion of the
sector mirror and the cutout portion at the rim of the mask into
the reference path. The beam of light from the other light source
emitting a continuous spectrum, for instance a deuterium lamp,
impinging upon the mask radially inwardly of the cutout thereof, is
interrupted by the mask and in this position cannot pass through
the cutout portion of the sector mirror into the sample path. In
another (third) position of the sector mirror and of the mask, the
light from the deuterium lamp passes through the completely open
sector of the mask and is reflected back therethrough by the
reflecting sector arranged on the "back" of the sector mirror into
the reference path. In a further (fourth) position of the sector
mirror the beam of light from the deuterium lamp passes through the
inner arcuate aperture of the mask and through the transmitting
portion of the sector mirror into the sample path, whereas
conversely the light from the hollow cathode lamp is blocked from
the reference path at this time by the non-transmitting rim of the
mask. The mask is arranged at such a distance behind the sector
mirror that the cross-section of the beam of light from the
deuterium lamp and the cross-section of the reference beam path are
discretely separated (i.e., in a non-overlapping manner) in the
plane of the mask and are thus separately controllable by the mask.
In this manner a highly simple assembly is obtained. It is not
necessary to arrange one light source between the sector mirror and
the mask, so that beams of light originating from both light
sources can be generated in substantially identical geometrical and
optical paths by conventional means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the path of rays as determined by the chopper
arrangement according to this invention;
FIG. 2 is a front view of the chopper assembly showing the sector
mirror mask; and
FIG. 3 is a block diagram of the signal analyzing arrangement.
In the embodiment according to FIG. 1, a beam of light 10
originating from a hollow cathode lamp (not shown) is focused by
means of a concave mirror 12 via a plane mirror 14 to a point 16 in
the vicinity of a chopper arrangement 18. A beam of light 20 which
originates from a light source (not illustrated) such as a
deuterium lamp emitting a continuous spectrum is focused by optical
elements (also not illustrated) at the point 22 on a deflecting
mirror 24 which then reflects the beam onto the chopper arrangement
18.
The chopper arrangement 18 contains a sector mirror 26 and a mask
30 rotating rigidly with the sector mirror about the same axis 28.
The mask 30 is arranged a spaced distance from the sector mirror
26, specifically on its "rear" side from which it is approached by
the beam of light 20 originating from the deuterium lamp. The two
points 16 and 22 in which the beams of light 10 and 20 are focused
are disposed symmetrically with respect to each other as related to
reflection of the beam 20 by the sector mirror in a plane
containing the axis of rotation 28 of the chopper arrangement 18,
wherein the beam axes are inclined with respect to the normal to
the surface of the sector mirror 26 in the direction towards the
axis of rotation 28. The cross-sections of the beams of light 10
and 20 coincide in the plane of the sector mirror 26 so as to be
substantially equal in size (and shape).
The sector mirror 26 contains two reflecting sectors 32 and 34 each
extending for approximately slightly less than 90.degree. (compare
FIGS. 1 and 2). The reflecting sectors 32 and 34 are arranged
diametrically opposite each other with respect to the axis of
rotation 28. The reflecting sector 32 is arranged on the side
facing the hollow cathode lamp (the front side of the sector) so
that it reflects the beam of light 10. The reflecting sector 34 is
mounted on the other (back) side of the sector mirror 26 facing the
deuterium lamp and the mask 30, and sector 34 reflects the beam of
light 20. Between the reflecting sectors 32 and 34 the sector
mirror 26 has completely transmitting or cutout portions 36 and 38
which extend for approximately 90.degree.. Between the reflecting
sector 32 and the cutout portion 38 and between the reflecting
sector 34 and the cutout portion 36 absorbing sectors 40 and 42,
respectively, each for generating a dark signal, are provided on
the reflecting side of the respective reflecting sector.
The mask 30, in the sector of the transmitting cutout portion 36,
has an arcuate aperture 44 which has its radial distance from the
axis 28 corresponding to the intersection point of the beam 20
through the plane of the mask 30 (see FIG. 1). Outside of this
aperture 44, the mask 30 has a nontransmitting rim or peripheral
portion 46. On the other hand, in the range of the transmitting
cutout portion 38 of the sector mirror 26 there is provided a
non-transmitting central portion 48 in the area of the intersection
point of the beam 20 and outwardly thereof a cutout portion 50. In
the range of the reflecting sector 34 the mask 30 has a completely
open cutout portion 51.
The described arrangement operates as follows. When the reflecting
sector 32 is in the lower position in FIG. 1 the beam of light 10
is reflected therefrom. It is then collected by a concave mirror 52
and is directed into a sample path 54 (which goes to the atomic
absorption sample). The beam of light 20 is masked at this time by
the mask 30. After about a 90.degree. rotation of the chopper
arrangement 18 (counter-clockwise as seen in FIG. 2) the cutout
portion 38 is at the bottom as seen in FIG. 1, and the beam of
light 10 is transmitted through the sector mirror 26, passes
through the peripheral cutout portion 50 of the mask 30 and is
collected by a concave mirror 56. The beam of light thus collected
is directed into a reference path 60 by means of a deflecting
mirror 58. However, the beam of light 20 is masked by the central
absorbing portion 48 of the mask 30 and cannot pass into the sample
path through the cutout portion 38. After another 90.degree.
rotation of the sector mirror 26 in a counter-clockwise direction
in FIG. 2, the beam of light 20 impinges upon the reflecting (back)
sector 34 through the cutout portion 51 of the mask and is
reflected by the same into the reference path 60; at this time the
opaque and absorbing other (front) surface of the sector 34 blocks
the beam 10 from going to either of the paths. In the last position
of the sector mirror 26, the beam of light 20 passes through the
arcuate aperture 44 (as shown in FIG. 1) and the cutout portion 36
of the sector mirror into the sample path 54. The beam of light 10
passing through the cutout portion 36 is interrupted by the
marginal portion 46 of the mask so that it cannot pass into the
reference path when the chopper is in this position.
Thus, with the described chopper arrangement the following
switching sequence is obtained:
a. beam of light 10 from the hollow cathode lamp goes to the sample
path;
b. beam of light 10 goes to the reference path;
c. beam of light 20 goes to the reference path;
d. beam of light 20 goes to sample path.
Therebetween, due to the absorbing sectors 40 and 42, respectively
and the mask 30, dark signals are respectively obtained,
specifically at the end of (a) and at the end of (c) above.
The arrangement would also function in an analogous manner if in
FIG. 1 the light sources and/or sample and reference paths of rays
were interchanged. It would also be possible to change the angular
arrangement (i.e., the circular order) of the sectors to each other
provided the association of the respective sectors of the sector
mirror and the mask is maintained. This would only lead to a change
in the above stated switching sequence.
FIG. 3 illustrates schematically the processing of the obtained
signals. Reference numeral 62 designates the line-emitting hollow
cathode lamp, and reference numeral 64 designates the deuterium
lamp emitting a continuous spectrum. The beams of light 10 and 20
are supplied alternately to the sample and reference paths 54 and
60, respectively, in the above stated switching sequence, a flame
66 (for atomizing the sample) being arranged in the sample path 54.
The beam of light 10 is attenuated by the flame 66 by the factor
(1-A.sub.0) (1-A.sub.1), A.sub.0 being the absorption of the
resonance line by the wanted element in the flame 66 and A.sub.1
the attenuation by the background absorption. The beam of light 20
is essentially only subjected to an attenuation caused by the
background absorption by the factor (1-A.sub.1).
The signals of the detector (not shown) are phase-sensitively
demodulated into the four intervals (a) to (d) above and are
therefore separately available. The signals from the sample path 54
are amplified by means of an variable gain amplifier 68 to which
they are applied via a controlled switch 70 during the intervals
(a) and (d).
During the intervals (c) and (d) a comparator-controller 72
compares the signal from the deuterium lamp 64 in the reference
path 60 with the output of the amplifier 68 which, for this purpose
connects to the controller input during the interval (d) via a
controlled switch 74, and controls the gain of the amplifier 68
accordingly (i.e., to make these signals equal). Thus, by varying
the gain of amplifier 68, the absorption loss due to background
absorption is compensated, i.e., the amplifier 68 amplifies the
signals by a factor ##EQU1## During the interval (a), switch 74
applies the amplifier output signal, which is proportional to:
##EQU2## (where I.sub.10, is the original intensity of beam 10) to
another controlled switch 76, which connects the signal to a
logarithmic amplifier 78. During the interval (b) the switch 76
connects the unattenuated signal originating from the beam of light
10 when passing through the reference path of rays (which signal is
at least proportional to I.sub.10) to the logarithmic amplifier 78.
The output of the amplifier 78 is amplified once more by a d.c.
amplifier 80 and supplies a signal proportional to: ##EQU3##
independently of I.sub.10, detector sensitivity or background
absorption.
A practically favorable construction consists in making the sector
mirror 26 in the form of a disk-shaped carrier of
light-transmitting material on which the reflecting sectors 32 and
34 are mounted as oppositely reflecting layers, and that these
reflecting layers are covered on the other side by an absorbing
layer. The mask carrier 30 may be a circular thin disk having
appropriate opaque and absorbing portions, the "aperture" or
"cutout portion", 44 and 50, respectively, and the entirely "open"
portion 51 being merely transparent portions of the disk. The disk
should be very thin in order to keep adjusting errors small.
* * * * *