U.S. patent number 3,748,833 [Application Number 05/234,617] was granted by the patent office on 1973-07-31 for sample valve for chromatographic apparatus.
This patent grant is currently assigned to The Foxboro Company. Invention is credited to Edwin L. Karas, Davis S. Lee, Robert A. Vanslette.
United States Patent |
3,748,833 |
Karas , et al. |
July 31, 1973 |
SAMPLE VALVE FOR CHROMATOGRAPHIC APPARATUS
Abstract
Chromatographic apparatus is described wherein the improvement
comprises a sample valve including slidably engaged members formed
of a hard, wear-resistant alumina lapped to a high degree of
flatness. These valve members are adapted to be molded using
relatively inexpensive techniques. The engaged surfaces of the
valve present cooperating ports and cavities which are adapted,
when the valve members are shifted from one position to another, to
inject a fixed amount of a sample mixture into a column. The valve
surfaces also are formed with grooves carrying a flow of carrier to
aid in isolating the injection ports from adjacent sample
ports.
Inventors: |
Karas; Edwin L. (Sharon,
MA), Lee; Davis S. (North Easton, MA), Vanslette; Robert
A. (Medfield, MA) |
Assignee: |
The Foxboro Company (Foxboro,
MA)
|
Family
ID: |
22882105 |
Appl.
No.: |
05/234,617 |
Filed: |
March 14, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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829576 |
Jun 2, 1969 |
|
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Current U.S.
Class: |
96/105 |
Current CPC
Class: |
G01N
30/20 (20130101); G01N 2030/204 (20130101) |
Current International
Class: |
G01N
30/20 (20060101); G01N 30/00 (20060101); B01d
015/08 () |
Field of
Search: |
;55/67,197,386
;210/31C,198C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Adee; John
Parent Case Text
This application is a continuation-in-part of our copending
application Ser. No. 829,576 filed on June 2, 1969. This invention
relates to chromatography. More particularly this invention relates
to a metering valve for injecting a precise amount of sample
mixture into a chromatographic column.
Claims
We claim:
1. In chromatographic apparatus of the type comprising a separation
column to which is connected a supply of carrier fluid to extablish
a continuous flow thereof through the column, the apparatus further
including a sample valve operable to inject into said flowing
carrier fluid a precisely metered amount of a sample mixture to be
separated into its constituent components by the column for
detection and determination of the concentration of at least one
component, said sample valve being of the type having first and
second members with interaction surfaces slidably engaged for
shifting movement between first and second positions, said members
being formed at said interaction surfaces with first passage means
cooperable in said first position to connect said carrier fluid
supply to said column to establish said continuous flow of carrier
thereto, said members being formed at said interaction surfaces
with second passage means cooperable in said first position to
connect a supply of sample mixture to a metering section to place
therein a predetermined amount of sample mixture, with at least a
part of said passage means being cooperable in said second position
to entrain the sample mixture from said metering section into the
flowing carrier fluid to be conducted through said column for
analysis;
the improvement in said apparatus wherein both said first and
second members, including said interaction surfaces thereof, are
made of a technical ceramic which is chromatographically inactive
and which comprises metal oxide of at least 80 percent purity
sintered to a dense mass at a sintering temperature of at least
about 1,100.degree. C and formed with said interaction surfaces
having a smoothness effectively eliminating any adsorbent effect of
the surfaces on the fluid samples.
2. Apparatus as claimed in claim 1, wherein said interaction
surfaces are lapped to a smoothness of less than about 15
micro-inches (RMS).
3. Apparatus as claimed in claim 2, wherein said surfaces are
finished to a smoothness less than about 5 micro-inches (RMS).
4. Apparatus as claimed in claim 1 wherein said metal oxide has a
density of at least 75 percent of its theoretical maximum
density.
5. Apparatus as claimed in claim 4, wherein said metal oxide has a
specific gravity of at least about 3.0 grams per cubic
centimeter.
6. Apparatus as claimed in claim 5, wherein said metal oxide has a
purity of greater than 95 percent and a specific gravity greater
than 3.5 grmas per cubic centimeter.
7. Apparatus as claimed in claim 6, wherein said metal oxide is
alumina.
8. Apparatus as claimed in claim 7, wherein said alumina has a
purity of about 99 percent.
9. Apparatus as claimed in claim 1, wherein said surfaces are flat
to within one wavelength of light.
10. Apparatus as claimed in claim 1, wherein said interaction
surfaces are free from lubricant.
Description
Chromatography is an analytical procedure of separating components
in a mixture by passing a sample of the mixture through a column
containing a material which retains the components for differing
periods of time. Thus, the individual components emerge at
different times from the column. A detector placed at the output of
the column provides an electrical signal in the form of a series of
peaks, each reflecting the concentration of a respective
component.
The chromatographic technique is capable of determining the
concentration of minute amounts of a component in the mixture. To
make fullest use of this capability, the sampling of the mixture
must be carried out consistently and accurately. Specifically, the
sample valve employed to inject a sample of the mixture into the
column must be essentially leakproof, and must be capable of
reliably metering a predetermined amount of sample each time it is
actuated. Moreover, the valve must be effectively "neutral" with
respect to the sample fluid. This is, the valve must not alter
passage of the sample through the input conduits (e.g., it must not
adsorb the sample), it must not react with the sample, and it must
not contaminate the sample with foreign matter, even of very tiny
amounts.
Over the past decade or so, a variety of different types of sample
valves have been devised, some of which have gone into extensive
commercial use. However, notwithstanding design efforts by many
people, none of the sample valves has turned out to be truly
satisfactory for the intended use. One of the principal problems
with available valves is excessive wear with usage, leading
ultimately to leaks requiring repair or replacement of the valve.
For example, in conventional valves with sealing surfaces formed of
stainless steel and Teflon, the valve may not last beyond 300,000
actuations without thereafter causing undue leakage. Moreover,
conventional sample valves are inordinately expensive to
manufacture. Thus, there has existed for some time an urgent need
for a new valve design providing important improvements in
longevity and reduced cost.
In a preferred embodiment of the invention to be described
hereinbelow in detail, there is provided a sample valve which will
operate without significant leakage for a substantially greater
number of operating cycles than conventional valves. This new valve
moreover is relatively inexpensive to make. The new valve
incorporates planar sealing surfaces molded of a specially selected
ceramic material, advantageously very hard, dense, and
smooth-surfaced alumina which has been found to be unusually well
suited for the chromatographic application, meeting all of the
stringent requirements discussed above, yet capable of being
manufactured at relatively modest cost.
The deterioration of prior art sample valves often arises from
scratching effects caused by small hard particles that get in
between the valve surfaces. The scratches in the valve surfaces
destroy the fluid tightness of the valve which then becomes unable
to provide an accurate sample for analysis, and permits leaks into
the column which create errors. The valve according to the
invention, however, provides an unusually long-lasting useful life
free from abrasion effects due to such dirt or other particles.
Accordingly, it is an object of the invention to provide superior
chromatographic apparatus including a relatively inexpensive sample
valve capable of reliably injecting a sample into a carrier stream
and operable over many cycles without deterioration. Other objects,
aspects and advantages of the invention will be understood from the
following description of a preferred embodiment of the invention
considered together with the drawings wherein:
FIG. 1 is a block diagram and perspective view of a sample valve in
accordance with the invention as used in connection with a
chromatographic instrument;
FIG. 2 is a perspective schematic representation of fluid sampling
port interconnections for the valve of FIG. 1;
FIG. 3 is a plan view of a valve slide employed with the valve of
FIG. 1;
FIG. 4 is a sectional view of the valve slide taken along line 4--4
in FIG. 3;
FIG. 5 is a plan view of a valve seat employed with the valve of
FIG. 1;
FIG. 6 is a sectional view of the valve seat taken along line 6--6
in FIG. 5;
FIG. 7 is a sectional view of the mounted valve slide and seat
taken along line 7--7 in FIG. 3; and
FIG. 8 is a plan view of the manifold employed with the valve of
FIG. 1.
With reference now to FIG. 1, there is shown chromatographic
apparatus 10 incorporating a sample valve 12 connected to a source
14 of carrier gas such as helium. The carrier gas is continuously
supplied through the valve 12 to a conduit 34 leading to a
chromatographic column schematically shown at 16. (In a practical
embodiment of the invention, the column 16 typically would consist
of a small-diameter tube, wound in compact configuration, but has
been shown as an upright element merely for illustrative
purposes.)
At the output of the column 16 is a detector 18, such as a
thermal-conductivity cell, to provide electrical signals
representative of the various components separated by the column.
The electrical signals are passed to a utilization device 20 which
may include an electronic integrator, memory, display, controller,
recorder and alarm, in various combination as needed for
utilization of the chromatographic measurement. The gases which
emerge from the column are vented at an exhaust port schematically
indicated at 22.
The chromatographic instrument operates by injecting in series with
the carrier gas stream flowing to the column 16 a preselected
amount of a mixture to be analyzed. A supply of the mixture is
illustrated at 24. The mixture gas in the embodiment of FIG. 1
flows continuously through a conduit 26 to the valve and thence
through another conduit 28 leading to a sample vent.
The valve 12 serves upon actuation to inject a precisely metered
quantity of the mixture into the carrier gas stream flowing through
conduit 34 to the column.
The valve 12 basically comprises two relatively slidable parts, a
valve slide 38 and a valve seat 40. Below the valve seat 40 is a
manifold 42 which interconnects the several conduits with ports
located in the valve interaction surfaces between the slide and the
seat. The valve seat 40 is secured to the manifold 42, as by means
of solder glass fusing, and the manifold in turn is supported by a
suitable housing (not shown).
The valve slide 38 and valve seat 40 are each formed of a hard,
wear-resistant material presenting interaction surfaces lapped to a
high degree of flatness and polished to a high degree of smothness.
The flatness after lapping is of the order of a quarter wavelength
of light, that is, about one to five millionths of an inch. The
preferred material is a ceramic comprising at least 80 percent pure
alumina, advantageously better than 90 percent pure alumina, the
remainder being a suitable binder such as glass silicate material,
or the like. Both interacting slide surfaces of the valve should be
made of the selected ceramic material. The finest results have been
achieved by using alumina which is at least 99.5 percent pure.
There are many different kinds of materials encompassed by the term
ceramic, and those particular kinds historically understood to
typify basic ceramic material, i.e., materials such as pottery clay
or glass, are not appropriate for use in a chromatographic valve.
Even more modern ceramics, including a number of categories of
alumina, are not suitable for achieving the high performance
required. For example, many types of alumina are
chromatographically active (i.e., adsorbent), and thus, if used as
the interface material in a chromatographic valve, would interfere
with the passage of the sample fluid through the valve.
To highlight this adsorbent characteristic of alumina, it may be
noted that alumina is well known in the art of chromatography as an
excellent packing material for chromatographic columns; see, for
example, "Principles of Adsorption Chromatography" by Lloyd R.
Snyder, 1968, pages 163-168. Certain classes of alumina also may
tend to react with the sample, as noted on page 357 of the
above-mentioned text by Snyder. Thus one considering the
application to chromatographic valves of ceramics such as alumina
would necessarily face serious difficulties with potentially
adverse characteristics for such application.
It has been found, however, that such serious problems can be
avoided by the use of specific ceramics which perform surprisingly
well when used as the interface material in a chromatographic valve
as disclosed herein. In more detail, now, the basic ceramic
material for this purpose should be a highly-pure sintered
crystalline metal oxide, and especially the poly-crystalline form
(of which alumina may be considered a principal representative).
Such materials have been referred to in the art as "technical"
ceramics, or "engineering" ceramics, reflecting the high purity of
metal oxide. One accepted standard is 80 percent pure metal oxide
or better.
The ceramic material must be chromatographically inert i.e., not
chromatographically active, and with respect to alumina this can be
achieved by using the so-called alpha alumina, fired at a
temperature above about 1,100.degree. C. The purity of the material
preferably is higher than 80 percent metal oxide, desirably as high
as 99.5 - 99.9 percent pure. The ceramic thus should be very dense,
i.e., tightly compacted crystals with very little binder (typically
glass) in the intercrystalline spaces. A specific gravity for
alumina of above 3.0 grams per cc. is an important characteristic
in this respect. As one example, an alumina of 80 percent purity
may typically have a specific gravity of about 3.4 grams per cc.
Ideally the specific gravity should be even closer to the
theoretical maximum value of about 3.98, typical for sapphire. In
general the density of the metal oxide used for the valve surfaces
should be above about 75 percent of the theoretical maximum and
preferably higher.
To eliminate any significant effect of sample adsorption (and
simultaneously to assure essentially leakproof operation of the
valve), the metal-oxide ceramic material must have an extremely
smooth surface, effectively free from pores, i.e., free from
cavities of any kind which might tend to temporarily trap particles
of the sample or other fluids passing through the valve. The
surface finish should be smooth to a value less than about 5
micro-inches (RMS); in some cases, a smoothness of less than one
microinch (RMS) will be appropriate. Such smoothness moreover tends
to reduce substantially the exposed surface area, and thereby
significantly minimizes any tendency of the material to adsorb the
fluid sample passing through. To obtain a dense and pure sintered
metal oxide, suitable for achieving the required smooth surface
finish, entails a quite high sintering temperature, e.g., above
about 1,100.degree. C, and preferably between 1,400.degree. and
1,800.degree. C.
There is some uncertainty about the exact mechanism responsible for
adsorption in a ceramic such as alumina. The adsorptive effect has
been considered possibly to be due at least in part to molecular
binding forces, of the type sometimes referred to as Van der Waal
forces. However, it has been found that this factor does not appear
to be predominant in the present application. If it were
predominant, or significant, the adverse effect of such forces
would tend to increase as the surface is made more smooth, e.g.
similarly to the known characteristic of smooth metal sliding
surfaces which tend to stick as a result of the so-called
"Jo-block" effect. However, experience with the present valve has
indicated that the adsorption effect of the ceramic interface
surfaces herein is minimized by providing highly smooth sliding
surfaces. Thus, it may be noted that high surface smoothness not
only provides improved leak-resistant characteristics, but also
advantageously achieves surprisingly superior performance from a
chromatographic analysis viewpoint, without detrimental adsorption
of sample fluid by the ceramic interface.
The mechanical properties of the valve material also are important.
The metal oxide ceramic should for example be very hard, e.g.,
above about 8.0 on Moh's hardness scale. The described alumina
(and, for example, the metal oxide berylia as well) has a hardness
of about 9.0 on that scale, providing superior wear and abrasion
resistance, as well as the capability of grinding down particles of
foreign matter which might enter between the sliding valve
surfaces. The ceramic also should have a high impact resistance,
preferably above 6.0 inch-pounds on the Charpy test. An alumina of
85 percent purity will have an impact resistance of about 6.3 inch
pounds, whereas certain electrical grade ceramics (such as
steatite) may have an impact resistance of only 4.5 - 5.0, and clay
ceramics may have impact resistances below about 3.5. The tensile
strength also should be very high, desirably above 20,000 psi.
Alumina of 99.5 percent purity has a tensile strength of about
28,000 - 32,000 psi, whereas the common electricalgrade ceramic
steatite has a strength of only about 8,500 psi, and stone ceramic
products even as low as 2,500 psi.
The valve slide 38 is reciprocably shiftable along an axis 36 as by
means of a suitable driver, such as a solenoid or air cylinder, not
shown in the drawing. This valve slide is provided with a spring
receiving recess 46 to receive a spring 48 used to urge the slide
onto the seat 40. In order to maintain the slide in lateral
alignment, the spring 48 acts at an inclined angle to the upper
surface 50 of the slide to maintain the side surface of the slide
in contact with an abutting cylindrical tube 52. The tube 52 is
supported by the valve housing not shown in the drawing, and is
made of the same material as the valve slide and seat.
The flatness and smoothness of the interaction surfaces between the
valve slide and seat assures a close and tight fit between them, so
as to effect a leakproof seal for the multiplicity of ports and
passages. The spring 48 aids in this, and also aids in assuring
that any particles which pass into the region between the valve
slide and seat will be ground or abraded away by the hard ceramic
interaction surfaces.
Referring now to FIGS. 2 and 3, the valve body 40 is formed with
four pairs of centrally-located vertical passages 62,72; 86,90 and
62',72'; 86',90' communicating between the manifold 42 and the top
face of the valve body. The first two pairs of passages 62,72;
86,90 are operative in injecting a sample into the column when the
valve slide 38 is shifted in one direction, and the other two pairs
62',72'; 86',90' are operative in injecting a sample into the
column when the slide is shifted in the other direction. That is,
the valve is double acting, by injecting a prefixed amount of
sample mixture when shifted in either direction. However, a single
acting valve is also contemplated by the invention.
Referring now also to FIGS. 5 and 6, the interaction face of the
valve slide 38 is formed with a plurality of spaced transverse
grooves 70,80; 70',80'; 88,88' adapted to connect together the
pairs of valve body passages 62,72; 86,90, etc., in either position
of the valve slide. In the position illustrated, groove 70 connects
passages 62 and 72, and groove 88 connects passages 86 and 90,
while the end groove 80 does not register with any passage. By
causing sample mixture to flow up through passage 62, across groove
70 and down passage 72, groove 70 serves in effect as a "metering"
section to store a predetermined fixed amount of sample available
at any time to be injected into the column. This sample mixture is
supplied through conduit 26 and manifold passage 66, and the flow
out is through manifold passage 76 to a vent (not shown).
While groove 70 is thus being supplied with a flow of sample
mixture, carrier gas simultaneously is flowing up through valve
seat passage 86, across the next adjacent groove 88 in valve slide
38, and down through valve seat passage 90 to the conduits leading
to the column 16. By shifting the valve slide to the left (FIG. 2),
groove 70 with its precisely metered amount of sample mixture is
brought into registration with passages 86 and 90. Thus the
continued flow of carrier through these passages entrains the
sample "slug" and forces it through the column for analysis.
The carrier gas flowing through groove 88 at injection station 54
comes from a manifold passage 82 connecting valve seat passage 86
to the carrier gas conduit leading to supply 14. The output of
injection station 54 is directed to the input of the other
injection station 56 by a horizontal manifold channel 94. Thus upon
shifting slide 38 to the left, the injected slug of sample from
metering section groove 70 follows the carrier gas path over to
injection station 56, up valve seat passage 86', traverses groove
88' (which replaces groove 70') and flows down through passage 90'
and an exit passage 94' out through conduit 34 to the column
16.
With the valve slide 38 in its leftward position, groove 70' is
supplied with sample mixture through vertical passages 62' and 72'
at sample station 58, venting from outlet passage 62' through
manifold passage 78 and sample vent 28. The sample mixture passing
up through inlet passage 72' is derived from conduit 26' leading to
conduit 26 and thence to mixture supply 24. Thus when the valve
slide is shifted back to its original position, this metered
quantity of sample moves into registration with passages 86',90' to
be entrained by the continuing flow of carrier gas and thereby
directed to the column 16 for analysis. The sample mixture
connected to passage 72' may be a supply separate from supply 24,
to provide redundancy assuring operation if one supply fails.
One of the important benefits of the valve construction described
herein is that the operative parts can readily be molded or cast
using relatively inexpensive known techniques. Thus, the valve seat
and the valve slide can be made in corresponding dies comprising
cavities into which may be placed the ceramic material as a powder,
to form the green mold. The bottom surfaces of the die have a
topography corresponding to the reverse of the desired shape of the
interacting valve surfaces, i.e., predominantly flat sections with
raised ridges to make the surface grooves and upstanding core
members to make the vertical passages.
This green form is fired at a high temperature in a furnace to
produce the hard ceramic parts. The flat interacting surfaces then
are lapped to a fine degree of smoothness and flatness. Continued
operation of the valve tends to improve the seal between the two
interacting surfaces, as a result of the self-lapping action of
planar surfaces. No lubricant is required between these surfaces,
nor are special wedge shapes needed for effective sealing.
In operation, the extremely hard alumina ceramic is not scored by
dirt, metal chips or other foreign material, as are the surfaces of
conventional chromatographic valves. Wear tests have indicated
actual improvement in the sealing surfaces. Such tests have shown
that at least about 2,000,000 are possible without developing the
usual leakage problems encountered in prior art chromatographic
valves. It is probable that even greater numbers of valve
actuations would be entirely practical if desired. The available
evidence suggests that valves in accordance with this aspect of the
invention will have a life which may be upwards of ten times that
of prior art valves.
The corrosion resistance of alumina is superior to stainless steel
used in some prior chromatographic valves, thus minimizing a
problem encountered in certain industrial applications. Such
ceramic also withstands higher temperatures than prior valves which
included valve surfaces of plastic such as Teflon. Because of this
high temperature capability, valves in accordance with the present
invention advantageously may, if the ports become clogged with
foreign substances, be cleaned simply by baking at an elevated
temperature, e.g. high enough to oxidize gum, varnish and tars to a
powder which may readily be removed.
A valve of this design may be quite compact, e.g., having an axial
length of about 1 inch and width of about three-fourths of an inch.
The stroke in a typical unit might be about 0.14 inches.
Preferably, resilient bumper stops are provided to cushion the
ceramic material from excessive shock at the end of each
stroke.
If liquid sample mixtures are being analyzed, capillary action may
tend to draw the sample material from the sample ports into the
carrier passages leading to the column. To avoid such undesired
contamination, the valve advantageously may be provided with what
might be termed fluid shields around the sample injection stations
54 and 56. These fluid shields are composed of interconnected
gutters through which carrier fluid from source 14 flows
continuously to drain so as to intercept any leaking sample fluid
and wash it away with the carrier. This carrier may be obtained
from a source having a higher pressure than source 14, but in any
event after passage through the shield is discarded through vents
and not used in the columns.
These gutters are formed in the interaction surfaces of the valve
slide 38 and valve seat 40 which cooperate to form enclosed
channels between the adjacent surfaces. These channels provide a
closed rectangular shield around each of the two sample injection
stations 54 and 56. The shields are operated in series, i.e.,
carrier first flows through one rectangular shield, then passes
through an interconnecting channel 114 in the manifold 42 to the
other shield, and from there to carrier vent passage 98 and vent
conduit 32.
Specifically in reference to the fluid shields, carrier gas at
either atmospheric or elevated pressure is first supplied from a
flow controlled source (not shown) through shield passage 100-102
in the manifold and valve seat respectively to a corner inlet port
104 in the valve seat. The carrier passes from the port 104 through
two separate paths to an opposite corner outlet port 106. One path
comprises a first gutter 108 which connects to a corner recess 110,
both being formed in the valve seat interaction surface; and a
second gutter 112 which is formed transversely in the valve slide
38 and provides a carrier passage between the corner recess 110 and
the corner outlet port 106. The second path includes transverse
gutter 112' formed in the valve slide to connect to a corner recess
110' formed in the valve seat 40, and a second gutter 108'
completing the path from the corner recess 110' to the outlet port
106.
From the corner outlet port 106, the carrier flows down through
interconnecting passage 113 and across channel 114 in the manifold
to corner inlet port 104' in the rectangular shield around the
other injection station 56. The arrangement of this shield is
similar to the first shield and thus will not be described in
detail.
From the view presented by FIG. 2, it will be appreciated that the
injection stations 54 and 56 are enclosed by fluid shields for both
positions of the valve slide 38. This result is obtained by
providing an additional transverse gutter 112' in the valve slide
which is so spaced from gutter 112' that upon valve actuation into
the alternate position the gutter 112" is placed where 112'
previously was located (at station 54) and 112' is placed where
gutter 112 was. In this manner gutter 112 is actually shared
between the two fluid shields.
The reason for locating part of each fluid shield in the slide and
the other part in the valve seat is to disconnect the moving gutter
passages from each other, thereby to prevent "short circuiting" the
sample ports directly to the injection ports during movement of the
valve slide. The gutters in the valve slide disconnect completely
from the valve seat gutters during transit so as to prevent
injecting fluid into (or removing fluid from) the injection
passages.
In some applications, it may be desirable to enhance the sealing
between the valve manifold 42 and seat 40 by a similar shielding
technique. Thus, as shown in FIG. 8, a fluid shield is formed in
surface 43 by etching a gutter 120 around the several ports. The
gutter 120 is fed with carrier at channel 122 communicating with
passageway 82 and the carrier in the gutter 120 is removed at
channel 124 leading to carrier vent conduit 98.
Although a specific preferred embodiment of the invention has been
described hereinabove in detail, it is desired to emphasize that
such detailed showing is for the principal purpose of illustrating
the invention, and is not to be considered as limiting the scope
thereof except as required by the prior art, it being understood
that numerous modifications of the structure and techniques will be
apparent to those skilled in this art. For example, although the
sample mixture metering section in the disclosed embodiment
consists of a groove in the valve slide, it will be apparent that
for larger samples it may be desirable to form vertical passages
through the valve slide to make connection to relatively large
volume metering tubes supported on the slide. It will also be
apparent that the use of fluid shields is not limited to liquid
applications, nor to the mixture metering valve only, but may be
beneficial to various types of column switching and backflush
valves as used in chromatographic instruments. For some
applications, the valve seat and the manifold may be provided with
additional passages to furnish a continuous flow of carrier gas
through groove 88' in order to assure that no contamination
accumulates in that groove. Furthermore, rotary instead of linear
valve slide action may be employed with ports and passages and
fluid shields correspondingly rotatably aligned. Other changes
within the scope of the invention will be obvious.
* * * * *