WO2005062036A2 - Verfahren und vorrichtung zur bereitstellung eines definierten fluidstroms, insbesondere für die flüssigkeitschromatographie - Google Patents
Verfahren und vorrichtung zur bereitstellung eines definierten fluidstroms, insbesondere für die flüssigkeitschromatographie Download PDFInfo
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- WO2005062036A2 WO2005062036A2 PCT/DE2004/002589 DE2004002589W WO2005062036A2 WO 2005062036 A2 WO2005062036 A2 WO 2005062036A2 DE 2004002589 W DE2004002589 W DE 2004002589W WO 2005062036 A2 WO2005062036 A2 WO 2005062036A2
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
- G01N2030/324—Control of physical parameters of the fluid carrier of pressure or speed speed, flow rate
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
- G01N2030/342—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient fluid composition fixed during analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/36—Control of physical parameters of the fluid carrier in high pressure liquid systems
Definitions
- the invention relates to a method and a device for providing a defined fluid flow, in particular for liquid chromatography.
- the splitting device 1 shown in FIG. 4 for a liquid chromatography device comprises a pump 3 for providing a defined total flow f 0 with a defined solvent composition.
- the pump 3 can contain devices for proportioning and mixing different solvents so that solvent gradients can be generated.
- the total flow f 0 supplied by the pump 3 is significantly higher than the desired (external) work flow f ew .
- the splitting device comprises a fluidic branch 5, which can be realized in the form of a T-piece, which divides the total flow fo into an internal workflow f lw and an internal excess flow f ⁇ e , and a fluidic resistor 7 in the working branch and a fluidic resistance 9 in the excess branch.
- the distribution ratio (workflow to excess flow) is determined by the ratio of the resistances.
- Resistor 7 is generally much larger than resistor 9, ie with the same pressure drop the internal work flow fi W is only a small percentage of the excess flow f le .
- the internal workflow f ⁇ w is also at the output 11 of the splitting device
- pressure sensors generally have relatively large internal volumes due to their design. Because of the compressibility of the solvents used and the elasticity of the pressure transducer, a flow flows to or away from the pressure sensor each time the pressure changes. As a result, the work flow is reduced or increased accordingly.
- the sensors in question measure the total pressure (relative to the ambient air or absolutely), they must have a measuring range of at least 200 bar. A measurement error of 0.05 bar therefore corresponds to an accuracy requirement of 0.025%. Such accuracy can only be achieved in practice with great effort.
- the object of the invention is therefore to provide a method for providing a defined liquid flow, in particular for liquid chromatography, which makes it possible to generate the workflow with high accuracy regardless of the counterpressure at the outlet, without a work sensor for detecting the pressure in the working branch and / or the river is needed.
- no pressure sensors should be considered flow-determining components are used.
- the invention is based on the object of proposing a device for implementing the method.
- the invention is based on the knowledge that an external, preferably very small, work flow can be achieved by a work device with sufficient constancy and reproducibility by measuring a compensating flow in a cross-branch between a work branch and an excess branch and by controlling the resistance value of a variable one fluidic resistance device can be regulated in the further course of the excess branch to a value of essentially zero or to a predetermined offset value which is low in comparison to the internal work flow. This means that the problematic measurement of the external work flow is not necessary.
- the predetermined offset value for the compensation flow can be chosen to be greater than zero, the positive sign indicating a flow direction from the work path in the direction of the excess path.
- the dependency of the sensor signal of the flow sensor on at least one property of the fluid, in particular the thermal capacity and thermal conductivity of the fluid can be corrected when regulating the compensating flow in such a way that the predetermined offset value for the actually flowing compensating flow results.
- the correction can be carried out in a simple manner in that a correction parameter is linked to the sensor signal for the correction, in particular a correction factor is multiplied by the sensor signal.
- the values for a correction factor can be saved in a lookup table.
- a functional dependency of the correction factor on at least one property of the fluid can of course be stored and evaluated for correction.
- the compensation flow for achieving a temporary reduction in the external work flow can be regulated in the further course of the work path to a predetermined value which is high in comparison to the offset value.
- a so-called “peak parking” can thus be achieved in HPLC. This means a temporary significant reduction in the
- the flow reduction can be achieved directly without additional components in that the compensation flow is temporarily not regulated to a value equal to or close to zero, but to a significantly higher, positive value.
- the resistance value of the changeable fluidic resistance device for determining the internal work flow and / or external work flow can be temporarily adjusted in the further course of the work path in such a way that a non-zero compensation flow results, and in this way the normal operating case expected internal work flow and / or external work flow can be determined from the signal of the flow sensor.
- the changeable fluidic resistance device for measuring the internal work flow in the transverse branch can be short-circuited and / or controlled to a value equal to zero, the transverse branch preferably having a fluidic resistance value equal to or close to zero.
- the compensation flow in the shunt arm is regulated to zero in the normal operating phase of the device, an external work flow then results which is equal to the measured internal work flow.
- the compensation flow is regulated to a low offset value, in particular in order to avoid a backflow of the fluid from the transverse branch into the work branch, the external work flow can be determined during the normal operation of the device from the difference between the internal work flow and the compensation flow be determined.
- the fluidic resistances determining the division ratio can be designed such that their fluidic throughput time is essentially the same. This has the advantage that even with a time gradient with respect to at least one property of the fluid, for example with regard to its composition and thus its viscosity, the distribution ratio remains constant (also over time) in any case.
- a similar effect can be achieved by designing the fluidic resistances which determine the distribution ratio in such a way that their fluidic throughput time is yours compared to the duration of conventional solvent gradients. In this case, it can be assumed with sufficient accuracy that the contradictions would almost always contain a fluid with the same solvent composition.
- the device according to the invention can be designed such that the total fluidic resistance value of the changeable fluidic resistance device is composed of the resistance value of an adjustable, preferably electrically controllable fluidic resistance element and a non-adjustable fluidic resistance element, the fluidic resistance value, in particular the non-adjustable fluidic resistance element Resistance elements, depends on the viscosity of the solvent used.
- the required setting range for the adjustable fluidic resistance element can be kept relatively small, as a result of which this element can be manufactured more easily and more cost-effectively.
- Such a device for influencing the pressure and / or flow conditions in a fluidic system can also be used independently of the device or independently of the method according to the present invention.
- Figure 1 is a schematic representation of an analog electrical block diagram of a device according to the invention with a constant flow pump.
- FIG. 2 shows a schematic illustration of a controllable, changeable fluidic resistance device for the device in FIG. 1; in the form of a development of an analog electrotechnical block diagram (Fig. 2a) and in the form of a schematic diagram for its implementation (Fig. 2b);
- Fig. 3 is a diagram illustrating the viscosity and pressure profiles of a device according to Fig. 1 with a resistance device according to Fig. 2 and
- Fig. 4 is a schematic representation of an analog electrotechnical block diagram of a device according to the prior art to explain the principle of the river division.
- the device 100 shown in FIG. 1 in the form of an analog electrotechnical block diagram for providing a defined fluid flow, in particular for liquid chromatography, to which a constant flow of the fluid supplied by a pump 1 is supplied, comprises a flow divider 5, which acts as a branching device T-piece can be formed, and fluidic resistors 7 and 9 in a working branch or an excess branch.
- a flow divider 5 acts as a branching device T-piece can be formed
- fluidic resistors 7 and 9 in a working branch or an excess branch.
- the resistance value of the fluidic resistors 7 and 9 is designated.
- the device 100 further comprises a fluidic branch 102 at the outlet of the fluidic resistor 7 and a fluidic branch 104 at the outlet of the fluidic resistor 9.
- the fluidic branches 102, 104 can again each be implemented as a simple T-piece.
- the device 100 has a transverse branch 106 which connects the fluidic branches 102 and 104 and in which a flow sensor 108 is arranged which supplies an output signal S ai which is dependent on the compensation flow f bal flowing in the transverse branch 106.
- an adjustable fluidic resistance device 110 is provided, which, as shown in FIG. 1, can be designed as a simple changeable and preferably electrically controllable fluidic resistor, for example as a controllable throttle valve.
- the device 100 comprises a control device 112 which controls the adjustable fluidic resistance device 110 with regard to its fluidic resistance value as a function of the signal S a i of the flow sensor 108.
- the signal flow is indicated in FIG. 1 by dotted lines.
- the pressure acting at this point can be detected on the fluidic branch 9 by means of an optional pressure sensor 114.
- the desired external work flow f ew is made available at the output 116 of the device 100, the ratio between the external work flow f ew and the total flow f 0 being to be kept constant with sufficient accuracy.
- the external excess flow f ee occurring at the output 118 of the device 100 is generally not used.
- the mode of operation of the device in FIG. 1 is explained in more detail below using the example of HPLC, only the components of an entire HPLC arrangement that are essential for the invention being shown:
- the arrangement like the known methods, is based on the principle of river division.
- the pump 3 supplies a defined, preferably constant, total flow f 0 with the desired, defined solvent composition to the device 100, to the outlet 116 of which the column (not shown) of the chromatography device is connected. Both the total flow f 0 and the solvent composition can also be variable over time.
- the total flow f 0 is converted by the flow divider 5 and the fluidic resistors 7 and 9 arranged in the working path and in the excess path into an internal excess flow fte and, as a rule, a substantially lower internal working flow f; w split.
- the distribution ratio is determined by the fluidic resistors 7 and 9 and the pressure drops across them. With a constant ratio of the resistors, the distribution ratio is constant when the pressure drops across the resistors 7 and 9 are always the same.
- the pressure sensor 114 serves to detect the pressure at the resistance device 110. Since the pressure drop in the transverse branch in the previously described mode of operation of the If device 100 is zero, this pressure also corresponds to the pressure at outlet 116 of the working branch. This pressure is not required to control or regulate the system, but is of interest in practice because it allows conclusions to be drawn about the condition (eg contamination) of the column connected there.
- An additional advantage of the arrangement according to the invention is that the internal workflow fj w supplied by the fluidic branch 5 and the fluidic resistors 7, 9, which in the previously described mode of operation is the same as the external workflow f ew, is checked or measured directly without additional components can be. As a result, both a blockage of the components of the fluidic branch 102 or the fluidic resistors 7, 9 and a malfunction of the pump 3 can be recognized. The measurement step required for this takes place independently of the normal operation of the system and is only used for checking or error analysis.
- a prerequisite for the measurement is a constant solvent composition, for which the sensitivity of the flow sensor 108, which depends in particular on the viscosity of the fluid, is known.
- the resistance value of the changeable fluidic resistance device 110 is reduced to a value of zero or almost zero.
- the pressure at the fluidic branch 104 or at the T-piece realizing it becomes equal to the external air pressure.
- the transverse branch which has a fluidic resistance value of zero or close to zero, the pressure at the fluidic branch 102 or the T-piece that realizes it also drops to the external air pressure.
- L0 direct flow b ai is therefore identical to the internal and external work flow in the
- the procedure described means a strong pressure change in the system. Because of unavoidable dead volumes in the system, it can take a long time to
- the fluidic resistors 7 and 9 are expediently designed in accordance with EP-A-0495 255 so that their internal volumes are approximately the same ratio as the two rivers. This results in the same fluidic cycle time for both resistors. This has the advantage that a change in the viscosity of the
- Solvent has the same effect on both branches, i.e. the allocation ratio remains constant in this case too.
- a similar effect can be achieved in that the internal volumes of the fluid resistors 7, 9 are kept low, so that the passage time of the solvent through the resistors is short compared to the duration of conventional solvent gradients.
- both resistors 7, 9 contain the same solvent composition, i.e. Changes in solvent viscosity have the same effect on both resistors.
- capillaries preferably made of quartz glass or metal.
- the desired volume and resistance ratios can be easily established or adjusted over a wide range.
- capillaries are characterized by a very good consistency of their properties.
- fluidic resistors which consist of porous materials (frits)
- the two flow-determining resistances de 7 and 9 always have the same temperature. For this purpose, it makes sense to install these resistors in a common housing, for example.
- the absolute temperature of these resistors plays a subordinate role, since both resistors change by the same factor.
- the regulating device 112 is intended to regulate the flow in the shunt arm to zero or to a predetermined low offset value (see below). Depending on the type of output signal from the sensor 108 and the control signal required to set the fluidic resistance device 110, this can be done in the simplest case by direct electrical coupling of the signals, for example via an amplifier, but better by an analog or a digital controller. Implementation as an integrating controller is particularly expedient, since in this way the mean time value of the flow in the transverse branch can be made zero with particularly good accuracy or can be kept at a constant value.
- the offset value must be selected so that its effect on the external work flow f ew can be neglected.
- the offset value expediently lies in a range between 0.2% and 5% of the external work flow f ew , for example in the order of magnitude of approximately 1%. This is particularly useful because the signal from the flow sensor 108 is usually solvent-dependent. Since the control device 13 tries to keep the signal from the sensor constant, the actual compensation flow f bal changes depending on the solvent composition. The resulting slight distortion of the external workflow f ew does not interfere with such small offset values.
- the solvent composition to be expected there is calculated from the solvent gradient and the current throughput time to the flow sensor 108.
- a correction factor for the sensor output signal is now determined on the basis of the known sensitivity curves of the sensor.
- the correction factors can, for example, be stored in a Lokup table.
- the actual compensation flow is then calculated from the sensor output signal and the correction factor. Any errors in this correction have a minimal impact on the external workflow f ew , since the offset value, as explained above, is usually only a small part of the workflow.
- the fluidic resistance of the components of the transverse branch has hardly any influence on the function of the arrangement in normal operation, since the flow in the transverse branch always has a value close to zero.
- the resistance value of the shunt arm should not be too high, however, as this would reduce the sensitivity of the control system.
- the fluidic resistance of the transverse branch must be designed to be as low as possible anyway, so that the compensating flow does not generate a pressure drop in the transverse branch.
- the flow reduction can be achieved directly without additional components, in that the compensation flow f ba i is temporarily not regulated to a value of zero or close to zero, but to a significantly higher, positive value.
- the external work flow f ew provided at output 116 is reduced by the set compensation flow f a i- Since the control device device 112 can set a precisely defined compensation flow, the external work flow f ew can be reduced to a precisely defined, adjustable value.
- the device 100 according to FIG. 1 thus offers the advantage that the external work flow f ew provided at the outlet 116 is independent of the back pressure of the devices connected there. Furthermore, the external workflow f ew provided is also independent of the solvent composition and its change. Even fast solvent gradients have no influence on the flow provided.
- the external work flow f ew provided always represents a precisely defined, constant part of the total flow f 0. This also applies to the solvent composition, apart from the time delay caused by the throughput time.
- the external work flow f e can thus be easily controlled in a precisely defined manner by changing the total flow.
- the flow sensors used to measure liquid flows are based on the
- the compensating flow f ba i in the shunt arm is not regulated to the value zero, but to a (low) offset value, in principle a flow sensor can be used which can only detect the amount and not the direction of the flow ,
- this pressure sensor 114 is arranged in the excess branch instead of in the working branch, the dead volume of the pressure sensor does not cause any problems. Since the pressure sensor also has no influence on the flow accuracy in the working branch, a simple, inexpensive design can be used. There are various possibilities for realizing the actuator, that is to say the changeable fluidic resistance device 110.
- One obvious solution is to use a variable "bottleneck", whereby the length and / or the cross section of the bottleneck can be changed.
- the pressure effective at the actuator is just as high as the pressure at the outlet 116 of the device (column pressure). This depends on the viscosity of the solvent and the type of chromatographic column. In practice, the pressure range is between about 30 and about 400 bar
- the column pressure can change
- the solvent composition at the two outputs of the flow divider is at all times (eg at branches 102 and 104) roughly the same. This means that the solvent that flows into the chromatographic column has the same viscosity as the solvent that flows into the actuator at the same time.
- the actuator is implemented as a series circuit consisting of a fixed and an adjustable fluidic resistance element.
- the fixed resistance element has a pressure drop that is slightly less than the pressure drop across the chromatographic column.
- the working range of the adjustable resistance element of the actuator only has to compensate for deviations from this theoretical case and pressure changes due to the contamination of the column.
- FIG. 2a shows an improved version of the adjustable, changeable fluidic resistance device 110 in the form of circuit symbols as well as a possible implementation in a schematic representation.
- the resistance device 110 is composed of two resistance elements 120 and 122, the fluidic resistance element 120 depending on the viscosity of the solvent flowing through.
- the fluidic resistance element 122 can be changed by the control device 112.
- the viscosity-dependent part 120 is symbolized by a long, thin capillary 124, the fluidic resistance value of which is directly proportional to the viscosity of the liquid.
- the adjustable part 122 is realized as an adjustable needle valve 126, wherein the needle can be moved by a motor drive 128 in such a way that the cross section of the passage changes.
- the resistance elements 120 and 122 can of course also be implemented in other ways.
- a compressible filter element or an elastic sealing element can also be used.
- the adjustable resistance element 122 does not have to have a linear behavior either: instead of a needle valve with motorized control of the needle, for example, a spring-loaded needle can be provided.
- the adjustable resistance element would be implemented as an adjustable pressure regulator. Its behavior corresponds approximately to that of an adjustable Zener diode in the electrical engineering analogue.
- Such an adjustable pressure regulator can also be understood as an adjustable resistor with a “bent” characteristic curve and is also subsumed in the context of this description under the term “changeable resistance device”.
- Such an adjustable pressure regulator can of course also be used without a non-adjustable resistance element to implement the adjustable resistance device.
- FIG. 3 shows, for a changeable fluidic resistance device 110 according to FIG. 2, the pressure profiles for a predetermined change over time in the viscosity of the solvent used.
- the pressure curves shown result for an arrangement according to FIG. 1, to the outlet 116 of which a chromatographic column is connected.
- the curve 202 is the predetermined course of the relative viscosity of the solvent mixture used, which is provided by the pump 3.
- Curve 200 shows the associated pressure curve at the chromatographic column, that is to say at outlet 116. Since the change in viscosity reaches the column only after a delay because of the passage time through resistor 7, the drop in viscosity becomes noticeably belated. In addition, the pressure curve appears smoothed, since the area with decreasing viscosity only gradually enters the column. Because of the transverse branch, the pressure at the resistance device 110, that is the sum of the Pressures at the resistance elements 120 and 122 equal to the pressure at the outlet 116 and thus also correspond to the curve 200.
- the curve 201 is the pressure drop at the fixed resistance element 120 of the resistance device 110, that is to say at the capillary 124.
- the course over time corresponds approximately to the curve 200.
- the capillary has a shorter throughput time than the column, so that the course is less smoothed or is delayed.
- curve 203 is the difference between the total pressure at the resistance device 110 (curve 200) and the pressure drop at the fixed resistance element
- the adjustable resistance element 122 of the resistance device must build up this pressure.
- the fixed resistance element 120 of the resistance device could be designed from the outset in such a way that its pressure drop corresponds exactly to that of the column. Then no regulation would be necessary at all and no cross branch would be required. In practice, however, this cannot be achieved with reasonable effort for various reasons. A major reason for this is that the column becomes locally dirty over time, which not only leads to a higher column pressure overall, but also changes the course of time.
- salts are sometimes used as chemical buffers. If the salt concentration is high, there is a risk that the salts will crystallize out. taping. If this happens in the resistance device 110, its function could be impaired.
- This problem can be avoided by providing the resistance device 110 on the low-pressure side with at least two additional connections for flushing. Through these additional connections, pure solvent (e.g. water) can be pumped through the actuator continuously or at certain time intervals. This reduces the salt concentration in such a way that crystallization is avoided or any existing salt crystals are dissolved and rinsed out.
- pure solvent e.g. water
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2006545903A JP2007515642A (ja) | 2003-12-23 | 2004-11-23 | 特に液体クロマトグラフィー用であって規定の流体流を供給するための方法と装置 |
US10/583,435 US7454959B2 (en) | 2003-12-23 | 2004-11-23 | Method and device for providing defined fluid flow, especially for use in liquid chromatography |
CA002551225A CA2551225A1 (en) | 2003-12-23 | 2004-11-23 | Method and device for providing a defined fluid flow, especially for use in liquid chromatography |
AU2004303921A AU2004303921A1 (en) | 2003-12-23 | 2004-11-23 | Method and device for providing a defined fluid flow, especially for use in liquid chromatography |
EP04802800A EP1697737A2 (de) | 2003-12-23 | 2004-11-23 | Verfahren und vorrichtung zur bereitstellung eines definierten fluidstroms, insbesondere für die flüssigkeitschromatogra phie |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10360964.4 | 2003-12-23 | ||
DE10360964A DE10360964B4 (de) | 2003-12-23 | 2003-12-23 | Verfahren und Vorrichtung zur Bereitstellung eines definierten Fluidstroms, insbesondere für die Flüssigkeitschromatographie |
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WO2005062036A2 true WO2005062036A2 (de) | 2005-07-07 |
WO2005062036A3 WO2005062036A3 (de) | 2005-10-06 |
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PCT/DE2004/002589 WO2005062036A2 (de) | 2003-12-23 | 2004-11-23 | Verfahren und vorrichtung zur bereitstellung eines definierten fluidstroms, insbesondere für die flüssigkeitschromatographie |
Country Status (7)
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US (1) | US7454959B2 (de) |
EP (1) | EP1697737A2 (de) |
JP (1) | JP2007515642A (de) |
AU (1) | AU2004303921A1 (de) |
CA (1) | CA2551225A1 (de) |
DE (1) | DE10360964B4 (de) |
WO (1) | WO2005062036A2 (de) |
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JP2012511725A (ja) | 2008-12-10 | 2012-05-24 | オールテック・アソシエイツ・インコーポレーテッド | クロマトグラフィーシステムおよびシステム部品 |
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US20140352822A1 (en) * | 2013-05-31 | 2014-12-04 | Eaton Corporation | Air bleed valve float arrangement with restrictor |
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JP2000274871A (ja) | 1999-03-19 | 2000-10-06 | Matsushita Refrig Co Ltd | 熱電装置、並びに、熱電マニホールド |
JP2001174094A (ja) | 1999-12-14 | 2001-06-29 | Matsushita Refrig Co Ltd | 熱電モジュールを内蔵するマニホールド |
US20040149011A1 (en) * | 2003-01-30 | 2004-08-05 | Stephen Staphanos | Valve-less on-line process gas chromatograph |
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2003
- 2003-12-23 DE DE10360964A patent/DE10360964B4/de not_active Expired - Fee Related
-
2004
- 2004-11-23 JP JP2006545903A patent/JP2007515642A/ja active Pending
- 2004-11-23 CA CA002551225A patent/CA2551225A1/en not_active Abandoned
- 2004-11-23 US US10/583,435 patent/US7454959B2/en not_active Expired - Fee Related
- 2004-11-23 EP EP04802800A patent/EP1697737A2/de not_active Withdrawn
- 2004-11-23 WO PCT/DE2004/002589 patent/WO2005062036A2/de active Application Filing
- 2004-11-23 AU AU2004303921A patent/AU2004303921A1/en not_active Abandoned
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US3271997A (en) * | 1963-01-17 | 1966-09-13 | Monsanto Co | Pneumatic denier monitoring apparatus |
US3282085A (en) * | 1963-03-29 | 1966-11-01 | Hastings Raydist Inc | Fluid operated filament diameter measuring device |
EP0380967A2 (de) * | 1989-01-25 | 1990-08-08 | Svg Lithography Systems, Inc. | Pneumatischer Sensor |
DE19914358A1 (de) * | 1999-03-30 | 2000-10-19 | Agilent Technologies Inc | Vorrichtung und Verfahren zur Bereitstellung von Volumenströmen von Flüssigkeiten in Kapillaren |
WO2003066264A1 (de) * | 2002-02-04 | 2003-08-14 | Extrude Hone Gmbh | Verfahren und vorrichtung zum erzielen eines bestimmten durchflusswiderstandes eines strömungskanals mit hilfe einer messbrücke |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008528970A (ja) * | 2005-01-21 | 2008-07-31 | ウオーターズ・インベストメンツ・リミテツド | 可変抵抗流体コントローラ |
Also Published As
Publication number | Publication date |
---|---|
DE10360964B4 (de) | 2005-12-01 |
US7454959B2 (en) | 2008-11-25 |
EP1697737A2 (de) | 2006-09-06 |
JP2007515642A (ja) | 2007-06-14 |
WO2005062036A3 (de) | 2005-10-06 |
US20070056357A1 (en) | 2007-03-15 |
DE10360964A1 (de) | 2005-07-28 |
CA2551225A1 (en) | 2005-07-07 |
AU2004303921A1 (en) | 2005-07-07 |
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