The invention relates to a high-pressure switching valve for high-performance liquid chromatography (HPLC).
In HPLC, a sample to be investigated has to be fed into a high-pressure liquid stream, wherein the latter should only be interrupted for as short a period of time as possible. For this purpose, high-pressure switching valves in the form of high-pressure injection valves are used which allow virtually interruption-free switching of the liquid stream. Such a structure is described for example in U.S. Pat. No. 3,530,721, the original application for which dates back to as early as 1965.
The further development of such an injection valve is mentioned for example in U.S. Pat. No. 4,242,909. The basic principle of the valve shown therein has become largely established in the meantime in HPLC. Since the present invention is based on this valve type, the principle is explained in more detail in the following text.
At this point, it should be mentioned that the valve according to
In the first switching position, shown in
In order to switch the valve into a second switching position, the rotor 106 can be rotated through 60° with respect to the stator 112 such that the grooves now connect together in each case those ports which previously had no connection. The direction of rotation is indicated in
Switching is usually executed by a motor-powered drive which can rotate the rotor 106 with respect to the stator 112. For the sake of clarity, the drive has been omitted in the drawings. In principle, switching of the valve can also take place manually, however.
The advantage of such valves is that they can be used for very high pressures, given a sufficiently high-pressure force F. Furthermore, the holes in the ports 118 can be arranged such that the ends lie on a circle with a very small radius. The grooves then likewise lie on a circle with a very small radius such that the dead volumes of the valve can be kept very small.
In HPLC, a trend toward separation columns having a small particle size has been observed in recent years. Such separation columns allow an improved separation performance and more rapid separation, for which reason the expression fast HPLC is used.
Since the flow resistance increases very greatly as the particle size drops, considerably higher pressures are necessary for fast HPLC. The maximum column pressure that occurs is typically between 100 and 400 bar in conventional HPLC, while 600 to 700 bar are usually necessary in fast HPLC, sometimes even over 1000 bar. A trend toward columns with an even better separation performance is already being observed, said columns requiring even higher pressures of up to about 2000 bar.
In order to be able to operate high-pressure injection valves at such high pressures, the pressure force F (see
This problem can be solved by an appropriate material selection or coating. Thus, a special coating which allows cost-effective production of rotor and stator and at the same time greatly reduces the wear of the materials is described in U.S. Pat. No. 6,453,946.
WO 2009/101695 describes a switching valve in which the stator is provided with a coating made of amorphous carbon (DLC coating) in order to improve stability. The end face or contact surface of the rotor consists of a synthetic resin.
However, it has been shown that although such improved valves behave more favorably, during operation at very high pressures, they nevertheless fail even after a relatively small number of switching cycles.
US 2010/0281959 A1 describes a switching valve suitable for high pressures, wherein the stator and/or rotor surfaces are provided with a DLC layer, wherein an adhesive layer is provided between each particular main body, which can consist of metal. However, when hard material is used in each case for the rotor and the stator, there is the risk that increased wear will occur on account of irregular surface pressure at the contact face, since hard main bodies scarcely deform at the contact face.
Therefore, it is the object of the invention to create a high-pressure switching valve for high-performance liquid chromatography, which has improved wear resistance and stability and can nevertheless be produced in an easy and cost-effective manner.
The invention is based on the finding that, unlike the conventional structure of such high-pressure switching valves, not only the stator is produced from a hard material but also the rotor. Suitable materials which are highly wear-resistant are in this case in particular metal, ceramic materials and glass. On account of the necessary high-pressure forces, such hard materials have not hitherto been used for the rotor and stator, since the high surface pressure at the contact face of the two parts can result in damage to the surfaces or even to breakage of the rotor or stator even at low manufacturing tolerances of the surfaces or slight incorrect positioning of the surfaces with respect to one another (e.g. in the event of tilting).
According to the invention, it is sufficient in this case if at least those regions of the rotor and stator at which the contact faces or end faces are formed consist of a hard material. Thus, the rotor and/or stator can also have parts made of a corresponding material, in particular insert parts on which the relevant end face is formed.
On account of the mounting of the stator or rotor, or of a relevant part connected thereto, with wobbling or tilting action according to the invention, it is possible to ensure that, in spite of the use of hard materials, a relative uniform surface pressure within the contact face is achieved during the rotary movement of the rotor, but in any case that the rotor end face 110 closely abuts the stator end face, wherein the hard materials ensure much improved wear resistance and stability.
Mounting the rotor with wobbling action with respect to the stator should be understood as meaning that a wobbling movement of the respective element about the rotational axis of the stator or about the axis of the valve takes place. Of course, as a result of the wobbling movement being allowed, the rotor and stator abut one another in every angular position of rotation, wherein a relatively uniform surface pressure over the entire abutment surface, but at least a surface pressure which is rotationally symmetrical about the axis, is additionally achieved.
According to one configuration of the invention, the rotor or the element connected to the rotor is mounted with wobbling action by means of at least one cushion-like element made of a material which is sufficiently soft and elastic to allow the wobbling movement and is also sufficiently rigid to generate the pressure force necessary for the sealing action. A suitable material is, for example, a polymer material, polyimide, polyamideimide or polyether ketone, in particular PEEK.
Rather than mounting the rotor with wobbling or tilting action, the stator can also be mounted in a corresponding manner. Since the contact face between the rotor and stator is located close to the rotational axis of the rotor, the stator has to be mounted radially outside this region, for example in that the stator end face or other faces of the stator which face the rotor rest on an annular element or on a plurality of cushion-like elements distributed around the circumference, said element or elements consisting of a suitable flexible material.
When the rotor is mounted with wobbling action, i.e. is mounted such that wobbling movements of the rotor are allowed, the at least one cushion-like element can be accommodated in an element or part of the drive for the rotor, said element or part being arranged on the side remote from the rotor end face.
In this case, it is appropriate to provide the at least one cushion-like element on or in an element or part of the drive which is driven in rotation and is coupled to the rotor for conjoint rotation. As a result, relative movements in the interface between the cushion-like element and the rotor do not occur or occur only to a very slight extent. At most, the wobbling or tilting movements of the rotor during its rotation can result here in such movements between the rotor and the cushion-like element which, however, are so slight that wear, in particular at the surface of the cushion-like element, can scarcely be expected.
That part of the drive that accommodates the at least one cushion-like element can have a plurality of engagement elements, preferably in the form of pins, which engage in recesses, preferably in the form of holes, in the rotor and couple the rotor in a force-fitting manner to that part of the drive that accommodates the at least one cushion-like element, wherein the engagement elements and recesses are formed such that they allow the wobbling movements or tilting movements of the rotor. In the simplest case, it is sufficient for the diameter of the holes, which extend preferably parallel to the rotational axis of the rotor, to be selected to be slightly larger than the outside diameter of the pins. Since positioning accuracy of about half of one degree is usually sufficient for the rotor, a corresponding clearance between the pins and the holes is readily acceptable.
In this case, the hole for the pin can be configured as a hole, in particular a stepped hole, that widens from the foot of the pin in the direction of the tip of the pin, wherein the inside diameter of the hole at the foot of the pin is only slightly greater than the outside diameter of the pin, that good positioning of the pin is achieved on the one hand, but on the other hand sufficient angular mobility of the pin is ensured. This is because, as a result of the hole widening in the direction of the pin tip, the upper region of the pin is not limited within a region of the acceptable and necessary pivoting movement or wobbling movement.
According to one configuration of the invention, the stator can consist of a metal body on which the port connections are formed and which accommodates a glass or ceramic insert part on which the stator end face is formed. This provides the advantage that the stator end face is also formed from a harder material, wherein the port connections can be formed in a simple, conventional manner in the metal part. Of course, in this case, a sufficient sealing action should be ensured between the two parts, in particular in the region of the transition of the ducts forming the ports from the metal part into the part consisting of the harder material. This sealing action can be achieved for example by adhesive bonding of the two parts or by the interposition of one or more sealing elements, wherein the two stator parts are pressed together by the pressing together of the stator and rotor, such that a sealing action is ensured as a result. Rather than one or a plurality of separate sealing elements, a thin plastics layer can be applied and thus firmly connected to one of the two parts at least in portions between the metal body and the insert part.
A suitable material for such sealing elements or sealing plastics layers is in particular polyether ketone, preferably PEEK.
Preferably, however, the sealing takes place via a plug unit which is inserted into the relevant port 118 and is screwed to the latter, wherein the capillary tip extends into the region of the insert part and provides sealing here.
According to a preferred embodiment, a hard, friction-reducing coating, preferably made of amorphous carbon (DLC coating), is applied to the stator end face and/or the rotor end face. Such a layer brings about a reduction in friction at the contact face between the rotor and stator.
Such a coating made of amorphous carbon can in particular be applied by plasma enhanced chemical vapor deposition (PECVD). By way of this process, a very uniform coating can be achieved, such that finishing is no longer required. A very good combination has been found to be the application of such a DLC coating to the end face of a ceramic rotor or stator or a part thereof.
According to one configuration of the invention, the stator end face can be formed in a planar manner in the region of contact with the rotor end face and the rotor end face can be formed in a slightly domed manner in the region of contact with the stator end face, or vice versa, in order to reduce the excessive increase in surface pressure in the peripheral region of the contact face. As a result, the amount of pressure force can be reduced, since the pressure force is distributed more uniformly over the contact face between the rotor and stator. Thus, at a particular necessary surface pressure at the contact face in the region of the port cross sections and grooves, the pressure force necessary for the production thereof can be reduced. In addition, on account of a reduced surface pressure in the peripheral region of the end face of the stator or rotor, wear is reduced.
The invention is explained in more detail in the following text with reference to an exemplary embodiment illustrated in the drawing, in which:
The high-pressure switching valve 100 illustrated schematically in
The rotor 106 of the switching valve 100, in the rotor end face 110 of which one or a plurality of grooves 108 are provided, interacts with a stator 112 which has a stator end face 114 in which port opening cross sections 116 of a plurality of ports 118 formed in the stator 112 open in the manner described at the beginning. The in each case other ends of the ducts forming the ports 118 are connected to only partially illustrated port connections 118a which provide for example a screw connection for connecting high-pressure capillaries. These may accommodate for example a capillary (not illustrated) which extends into the front, narrowed region of the relevant port connection 118a and is pressed against the latter in a sealing manner, for example by means of a plug part that can be screwed into the region 118a.
The basic mode of operation of the high-pressure switching valve 100 illustrated in
The stator 112 of the high-pressure switching valve 100 illustrated in
The upper part, facing the rotor 106, of the driven part 122 has a cylindrical shape and has, on its end face facing the rotor 106, a plurality of engagement elements 124 in the form of pins which extend parallel to the axis A. The engagement elements 124 engage in correspondingly formed holes 126 in the rotor 106 which, as illustrated in
As illustrated in
In the case of the embodiment illustrated in
An inner stator part 112b, which is accommodated in the outer stator part 112a and on which the stator end face 114 is also formed, can be produced from a hard material, in particular from ceramic. Of course, it is necessary to form the relevant parts of the ducts forming the ports 118 in this ceramic part, said ducts opening into the corresponding port opening cross sections in the stator end face 114.
The use of an inner stator part 112b consisting of hard material instead of a stator 112 consisting entirely of the hard material provides the advantage that the port connections can be produced in simpler manner.
Since the stator end face 114 consists of a hard material, such as ceramic, corresponding wear resistance and stability of the high-pressure switching valve 100 are achieved.
The inner stator part 112b can be pressed into a corresponding recess in the inner side of the outer stator part 112a. However, this is not absolutely necessary. Rather, as illustrated in
In addition, the inner stator part 112b is fixed securely in the housing by the application of a high-pressure force which is produced by the pressure unit 128 and is transmitted to the inner stator part 112b by the driven part 122 of the drive 104 and the rotor 106.
It would thus not be absolutely necessary for the stator part 112b to be supported on the housing part 120. Rather, the stator part 112b can also be securely fixed in its position just by the pressure force which is exerted via the rotor 106 onto the stator 112.
The ensuring of a sufficiently precise radial position of the stator part 112b or of the stator 112 is ensured by the recess in the outer stator part 112a, into which recess the inner stator part 112b can be inserted with a precise fit, and by the sufficiently exact radial positioning of the stator as a result of the connection to the housing part 120.
In order to achieve high wear resistance and stability, the rotor 106 of the high-pressure switching valve 100 is likewise produced from a hard material, preferably from ceramic. As a result, a rotor end face 110 and a stator end face 114, which each consist of hard material, interact with one another. Since such hard materials have only extremely low elasticity, which is not sufficient to compensate usual tolerances during the manufacturing and mounting of the high-pressure switching valve, in particular tilting of the rotational axis A of the rotor with respect to the normal to the stator end face 114, given a conventional construction of the high-pressure switching valve there would be a high risk that, at the high necessary surface pressure or the high pressure force which is exerted via the rotor 106 onto the stator 112, the stator end face 114 and/or the rotor end face 110 would be damaged, in particular during the rotary movement of the rotor 106.
For this reason, the underside, i.e. the end side, remote from the rotor end face 110, of the cylindrical rotor 106 is not acted upon directly by the end face of the rotationally driven part 122 of the drive 104, but via a cushion-like element 130. The cushion-like element 130 consists of a sufficiently soft and elastic material to allow a wobbling movement or tilting movement of the rotor 106 during its movement about the axis A. However, the material of the cushion-like element 130 is sufficiently rigid to transmit the pressure force necessary for the sealing action at the contact face between the rotor 106 and stator 112. The cushion-like element 130 is accommodated in an axial recess in the rotationally driven part 122 of the drive 104 in the embodiment illustrated in
The material of the element 130 can be a sufficiently firm or hard and yet elastic plastics material, for example a polyether ketone. In particular, the part 130 can consist of PEEK. Of course, the coupling between the driven part 122 and the rotor 106 by means of the engagement elements 124 and the recesses or holes 126 interacting therewith also has to be configured such that the wobbling movements are enabled to a sufficient degree. To this end, the inside diameter of the holes 126 can be selected to be larger by a corresponding degree than the outside diameter of the engagement elements or pins 124. Such a clearance between the engagement elements 124 and the recesses 126 is acceptable also with regard to sufficiently exact angular positioning of the rotor 106.
As can be seen from the enlarged detail according to
Of course, the desired wobbling movement of the stator 106 when hard materials are used for the rotor and stator can also be achieved by means of other constructions. For example, instead of a single axially arranged cushion-like element 130, a plurality of cushion-like elements arranged around the circumference of a coaxial circle in the end face of the part 122 may also be used. Instead of a cushion-like element made of plastics material, it is likewise possible to use other means that ensure corresponding movability of the rotor 106, for example spring elements made of metal (spiral springs, plate springs, solid-body joints etc.).
The construction, illustrated in
In order to reduce the friction between the stator end face 114 and the rotor end face 110, the use of what is known as a DLC coating on one of the two surfaces or on both surfaces has been found to be advantageous.
Although such a coating on a hard surface of a stator is known in the prior art, in this case an element made of a synthetic resin is used as rotor. Since the interaction of different materials and coatings on surfaces made of particular materials frequently entails surprising effects for reducing friction and for creating surfaces which are as wear-resistant as possible, it was thoroughly surprising that such a DLC coating is advantageous both for the stator 112 and for the rotor 106 when hard materials, in particular ceramics, are used.
Such a DLC layer was applied using a plasma enhanced chemical vapor deposition (PECVD). As a result, an extremely uniform coating with a constant thickness was produced. The application of such a DLC layer to a ceramic surface which is as planar as possible thus results in an extremely planar and smooth stator end face 114 or rotor end face 110.
A further improvement in the region of the contact face between the rotor 112 and the stator 106 can be achieved in that one of the two surfaces, in the construction according to
A slightly domed formation (optionally with different radii) of the stator end face 114 can thus contribute firstly to reducing the necessary pressure force F between the rotor and stator (in order to ensure a sealing action) and secondly to avoiding extremely high surface pressures in the radial peripheral region, which may in this region result in increased wear or in destruction of the surfaces and possibly of the entire parts.
Thus, the invention creates a high-pressure switching valve which has improved wear resistance and stability on account of the use of hard and optionally also brittle materials for the rotor and stator in conjunction with the allowing of wobbling movements for the rotor. An additional coating on one or both of the end faces of the rotor and/or stator can have an additional advantageous effect in relation to the wear resistance and the frictional action between the two parts. A domed formation on one of the two end faces results in further reduced surface pressure in the radial peripheral region and thus likewise increases the wear resistance.
Of course, the invention is not limited to the exemplary embodiment illustrated in
In order to achieve appropriately flexible mounting of the stator, the embodiment according to
Furthermore, a thin layer or a separate thin element can also be provided between the inner stator part 112b and the outer stator part 112a, said thin layer or separate thin element being elastically or plastically deformable such that tolerances between said parts or irregularities on the surfaces thereof can be compensated. In addition, a sealing action at the transition between the ducts forming the ports 118 can be achieved here at the transition from the part 112b to the part 112a or vice versa.
The thickness of the layer or of the separate part and the elasticity thereof can also be selected such that, with the sealing action being maintained, the part 112b is mounted with wobbling action in the part 112a. In this case, however, the part 112b should not, as illustrated in
The rotor can be formed in a two-part form both in such an embodiment and in the embodiment illustrated in
Number | Date | Country | Kind |
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10 2011 000 104 | Jan 2011 | DE | national |
This application is a Continuation-in-Part of U.S. patent application Ser. No. 13/979,407 filed Jul. 12, 2013 and entitled HIGH-PRESSURE CONTROL VALVE FOR HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY, which is a National Stage of International Patent Application No. PCT/DE2011/075325 filed Dec. 29, 2011 and published as WO 2012/095097 on Jul. 19, 2012, which claims priority to German Patent Application No. 10 2011 000 104.2 filed Jan. 12, 2011, the entire contents of which applications is incorporated herein for all purposes by this reference.
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Number | Date | Country | |
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20170284980 A1 | Oct 2017 | US |
Number | Date | Country | |
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Parent | 13979407 | US | |
Child | 15625691 | US |