CN115815234B - Needle washing device and needle washing method - Google Patents
Needle washing device and needle washing method Download PDFInfo
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- CN115815234B CN115815234B CN202111112883.1A CN202111112883A CN115815234B CN 115815234 B CN115815234 B CN 115815234B CN 202111112883 A CN202111112883 A CN 202111112883A CN 115815234 B CN115815234 B CN 115815234B
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Abstract
本发明属于分析仪器领域，提供了一种洗针装置及洗针方法，该洗针装置包括放电管和高频高压发生器，所述放电管为中空绝缘管，所述放电管外侧设置有第一电极，所述第一电极与所述高频高压发生器连接；所述放电管外侧设置或者不设置第二电极，所述第二电极与所述第一电极间隔设置。本发明的洗针过程涉及由于等离子体的产生引起化学降解和针体表面或内部骤热造成解吸附和蒸发，在多种效应同时作用下残留在进样针内外表面的样品瞬时被清除干净。
The present invention belongs to the field of analytical instruments, and provides a needle washing device and a needle washing method, the needle washing device comprises a discharge tube and a high-frequency high-voltage generator, the discharge tube is a hollow insulating tube, a first electrode is arranged outside the discharge tube, and the first electrode is connected to the high-frequency high-voltage generator; a second electrode is arranged outside the discharge tube or not, and the second electrode is arranged at an interval with the first electrode. The needle washing process of the present invention involves chemical degradation caused by the generation of plasma and desorption and evaporation caused by sudden heating of the needle surface or inside, and the sample remaining on the inner and outer surfaces of the injection needle is instantly cleaned under the simultaneous action of multiple effects.
Description
Technical Field
The invention belongs to the field of analytical instruments, and particularly relates to a very rapid sample injection needle washing device and a needle washing method.
Background
Analytical chemistry instruments typically include one or more sample injection needles for quantitatively drawing a sample from a sample holding container and then transferring the drawn sample to a detector for analytical detection. The residue of the sample on the needle can cause contamination and signal interference of the previous sample to the next sample, thus requiring cleaning of the needle between completion of sample introduction of one sample and aspiration of the next sample. Conventional needle washing processes are usually repeated washing with a needle washing liquid, which consumes fast and is not suitable for long storage, and a proper needle washing liquid is often required to be prepared for different samples. Throughout the analysis, needle washing is often the most time consuming step, typically several times longer than the sum of the aspiration and the injection. For traditional analytical testing procedures, although the needle wash takes a long time, the needle wash process is typically carried out with the sample testing process, so the problem is not significant, only additional preparation of the needle wash is required. However, for rapid detection systems, such as various direct spectroscopic, mass spectrometric and electrochemical analytical detection instruments, the detection time is only one to several seconds, the needle washing process is far longer than the detection time, and the flux (efficiency) of the instrument is limited by the needle washing step. Therefore, speeding up the needle washing procedure is one of the problems to be solved by the analytical instrument.
The development direction of the current mass spectrometry technology is in-situ ionization, microsampling, rapid analysis, movable field detection and the like. For example, microprojection electrospray ionization (MicroProbe Electro Spray Ionization, mupesi) is a special case of this development, and mupesi is introduced into a sample through the exterior of a solid needle tip, and the sample on the tip is ionized by high-voltage spraying to achieve mass spectrometry. The muPESI ion source can simplify the sample processing steps, accelerate the sample analysis speed (10 per min), and does not use carrier gas and mobile phase, so that the advantages are obvious. However, since μpesi is an ionization directly on very small amounts of sample by electrospray, the effect of a small sample residue on the next sample signal is very pronounced, typically exceeding 30%. Thus, the problem of residue is particularly serious for such micro-spray techniques, and thus development of needle washing techniques for such spray needles is necessary.
Sample injection needles for analytical detection are mainly of two types, capillary hollow needles and surface adsorption solid needles. The residue after sampling by the sample needle mainly occurs at the part of the sample needle contacting the sample. For hollow needles, residues are mainly present on the inner wall of the needle, the traditional needle washing method is to repeatedly suck and squeeze needle washing liquid by a needle cylinder, a liquid suction opening and a liquid squeezing opening are generally separated, and the needle washing efficiency is improved by matching one opening with a switching valve, and the needle washing liquid is sucked and spitted in flowing needle washing liquid, but the consumption of the needle washing liquid is larger in the mode. The sucking and spitting type needle washing consumes needle washing liquid and is long in time consumption, and residues can be sucked into the pipeline in the liquid sucking process, so that the pipeline connected with the sample injection needle is gradually polluted, and therefore, the pipeline generally needs to be replaced periodically. The surface adsorption metal needle is mainly soaked or flow washed to clean the residue.
The needle washing mode is long in time consumption and large in needle washing liquid consumption, and needle washing effects are different for different objects to be detected, so that proper needle washing liquid is required to be screened through experiments for specific objects to be detected. On the other hand, in order to improve the needle washing efficiency of the sample injection needle, ultrasonic waves or other more complex washing techniques are sometimes added in the needle washing process, which inevitably increases the complexity and cost of the washing device. Along with the development of analytical instruments in a high-flux direction, the existing needle washing mode becomes a bottleneck of technical development, and the needle washing technology of the microsyringe needle is in urgent need of improvement.
Disclosure of Invention
In order to solve the problems, the invention provides an extremely rapid sample injection needle washing device and a needle washing method, which are used for rapidly washing needles by means of alternating voltage of double electrodes by combining a dielectric barrier discharge principle. The needle washing process of the invention relates to chemical degradation of residual samples caused by plasma generation and desorption and evaporation caused by needle surface flash heat, and the samples remained on the inner and outer surfaces of a sample injection needle are instantaneously cleaned under the simultaneous action of multiple effects.
The technical problems of the invention are solved by the following technical scheme:
The needle washing device is used for washing sample residues on a sample injection needle, wherein the sample injection needle is used for sample injection of an analysis sample, the needle washing device comprises a discharge tube and a high-frequency high-voltage generator, the discharge tube is a hollow insulating tube, a first electrode is arranged on the outer side of the discharge tube and connected with the high-frequency high-voltage generator, a second electrode is arranged on the outer side of the discharge tube or not, and the second electrode is arranged at intervals with the first electrode.
Further, the discharge tube is a quartz tube, a ceramic tube, a glass tube, a carbon fiber tube or a glass fiber tube.
Further, the first electrode and the second electrode are respectively conductive coatings or metal foils.
Further, when the first electrode and the second electrode are simultaneously arranged on the outer side of the discharge tube, the interval between the two electrodes is set to be enough to ensure that no breakdown discharge is generated on the outer side of the discharge tube after high-frequency high voltage is applied.
Further, the output frequency of the high-frequency high-voltage generator is 1.5 kilohertz to 1 megahertz, and the output voltage is 1 kilovolt to 10 kilovolts.
Furthermore, when only the first electrode is arranged on the outer side of the discharge tube, the sample injection needle is made of a conductive material and is connected with the high-frequency high-voltage generator to form another electrode, and the tail end of the needle point of the sample injection needle is arranged in the area surrounded by the first electrode or near the upper edge of the first electrode.
Further, when a second electrode is arranged on the outer side of the discharge tube, the second electrode is connected with the high-frequency high-voltage generator, the second electrode is located below the first electrode, the sampling needle penetrates through the area surrounded by the first electrode, and the tail end of the needle tip of the sampling needle is arranged in the area surrounded by the second electrode or near the upper edge of the second electrode.
The invention also provides a needle washing method of the sample injection needle, wherein the sample injection needle is used for analyzing sample injection of a sample, one end of the high-frequency high-voltage generator is communicated with the first electrode, the other end of the high-frequency high-voltage generator is communicated with the second electrode or the sample injection needle, and dielectric barrier discharge occurs on the surface or inside of the sample injection needle for cleaning the residual sample on the surface or inside of the sample injection needle.
Further, when the other end of the high-frequency high-voltage generator is communicated with the second electrode, the sample needle penetrates through the area covered by the first electrode from top to bottom, and the tail end of the sample needle tip is arranged in the area covered by the second electrode or near the upper edge of the second electrode.
Preferably, when the sample injection needle is a hollow sample injection needle, air flow passes through the inside of the sample injection needle during dielectric barrier discharge.
Preferably, the dielectric barrier discharge time is 0.3-20 seconds.
Compared with the prior art, the invention has the beneficial effects that:
(1) The speed is extremely high, the residue of any sample injection needle can be reduced to below 1% in 1-10 seconds, and the sample injection needle dipped on the surface can be cleaned to be lower than 1% in 0.5-3 seconds, so that a technical bottleneck is broken through for the development of an analysis instrument in the high-flux direction;
(2) Suitable for various types of sample injection needles, including push-in type injectors (or manual sample injection needles), introduction type pipe sample injection needles, sample injection spray needles with coatings or grooves on the surfaces, and the like;
(3) No solvent consumption, pollution reduction, time saving for preparing the needle washing solvent, and avoiding error caused by light consumption of the needle washing solvent in the automatic operation process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention.
FIG. 1 is a schematic diagram of a solid sample needle washing device provided by an embodiment of the application, wherein a discharge tube is wrapped by two sections of electrodes;
FIG. 2 is a schematic diagram of a solid sample needle washing device with a discharge tube wrapped by a section of electrode according to an embodiment of the present application;
FIG. 3 is a schematic diagram of a hollow sample needle washing device with a discharge tube wrapped by two sections of electrodes according to an embodiment of the present application;
FIG. 4 is a schematic diagram of a hollow sample needle washing device with a discharge tube wrapped by a section of electrode according to an embodiment of the present application;
the drawing shows a discharge tube 1, a needle inlet 11, an air inlet 12, an electrode 2, a first electrode 21, a second electrode 22, a power supply 3, a sample injection needle 4, a solid sample injection needle 41, a hollow sample injection needle 42, a hollow branch pipe 5, a sealing cap 6 and a sealing gasket 7.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention aims to provide an extremely rapid sample injection needle washing device and a needle washing method, which are used for rapidly washing needles by means of alternating voltage of double electrodes by combining a dielectric barrier discharge principle. Experiments prove that the needle washing method provided by the invention can wash the residue to be within 1% in one second for most of the residual samples (namely, more than 99% of the residue is washed). The normal needle washing generally only reaches less than 5% of residues to meet the requirement of most instrument analysis, but only needs about 0.5 seconds to reach less than 5% of residues by using the invention, and no needle washing liquid is needed in the needle washing process.
The embodiment of the invention provides a microscale sampling needle washing device and a microscale sampling needle washing method, wherein the sampling needle is used for sampling an analysis sample and can be a hollow sampling needle or a solid sampling needle. Specifically, the sample needle washing device comprises a discharge tube, wherein the discharge tube is made of an insulating material, and the discharge tube can be a tube with one end closed or a tube with two openings. The discharge tube is provided with at least a first electrode outside, the first electrode is connected with a high-frequency high-voltage generator, a second electrode is optionally arranged (arranged or not) outside the discharge tube, and the second electrode is connected with the high-frequency high-voltage generator. Specifically, when only one electrode is arranged on the outer side of the discharge tube, the sample injection needle is connected with the high-frequency high-voltage generator to form the other electrode.
Specifically, when 2 electrodes are arranged on the outer side of the discharge tube, the interval between the two electrodes (between the lower edge of the first electrode and the upper edge of the second electrode) must be enough to ensure that no breakdown discharge is generated outside the discharge tube after high-frequency high voltage is applied, the two electrodes are respectively connected with two ends of the high-frequency high-voltage generator, and the needle tip of the sample injection needle is positioned in the area surrounded by the second electrode or near the upper edge of the second electrode.
The embodiment of the invention also provides a method for cleaning the sample injection needle, wherein the sample injection needle is used for sample injection of an analysis sample, one end of a high-frequency high-voltage generator (power supply) is communicated with the first electrode, the other end of the high-frequency high-voltage generator (power supply) is communicated with the second electrode or the sample injection needle, and dielectric barrier discharge occurs on the surface or inside of the sample injection needle for cleaning the residual sample on the surface or inside of the sample injection needle. When the two electrodes are arranged, the sample injection needle is not communicated with the power supply, at the moment, the sample injection needle penetrates through the area covered by the first electrode from top to bottom, and the tail end of the needle point of the sample injection needle is arranged in the area covered by the second electrode or near the upper edge of the second electrode. The dielectric barrier discharge time may be 0.3 to 20 seconds, preferably 0.5 to 5 seconds.
The application provides a very rapid sample injection needle washing device and a needle washing method, which utilize a dielectric barrier discharge principle to rapidly wash a sample injection needle by means of double-electrode alternating voltage. Experiments prove that the needle washing method provided by the application can wash the sample residues to be within 1% for most substances only by one second (namely, more than 99% of the sample residues are washed). The normal needle washing generally only reaches less than 5 percent of residues to meet the requirement of analysis of most instruments, but the needle washing process only needs about 0.3 seconds to reach less than 5 percent of residues by using the application, and no needle washing liquid is needed in the needle washing process. The application of plasma is quite a lot, but up to now, no precedent for cleaning the sample injection needle by the method has been reviewed.
Referring to fig. 1, a first embodiment of the present invention provides a needle washing device, which includes a discharge tube 1, an electrode 2 (including a first electrode 21 above and a second electrode 22 below, which are spaced apart by a certain distance), a power source 3, and a sample injection needle 4, wherein the power source 3 provides high-frequency voltage to the first electrode 21 and the second electrode 22, the tube body of the discharge tube 1 is made of an insulating material for blocking the current conducted by the electrode 2, dielectric barrier discharge occurs between the two electrodes when the first electrode 21 and the second electrode 22 are energized by the power source 3, and a sampling portion (i.e., a portion where a sample remains) of the sample injection needle 41 is placed in the discharge field, so that the residual sample on the sample injection needle 41 can be rapidly and thoroughly washed. The sample injection needle in this embodiment may be a solid sample injection needle or a hollow sample injection needle.
The proportions shown in the drawings are illustrative only and are not intended to limit the size of the associated parts.
Specifically, in fig. 1, the sample injection needle is a solid sample injection needle 41, the discharge tube 1 is a hollow insulating tube with two openings at two ends, the inner diameter is the lowest to allow the solid sample injection needle 41 to freely enter and exit, that is, the inner diameter needs to be larger than the maximum outer diameter of the sample injection needle, the inner diameter is generally 1-20 mm, preferably 1-2 mm, and is made of any solid insulating material which can withstand short-time high temperature and keep nonconductive, non-deforming and stable in mechanical performance, preferably a quartz tube, a ceramic tube, a glass tube, a carbon fiber tube, a glass fiber tube and the like. The electrodes 2 are arranged on the outer surface of the discharge vessel 1 in a tightly packed manner, mainly in three ways, namely 1) arranged as a metal coating or a graphite coating, 2) metal foil adhered to the discharge vessel 1 in a conductive adhesive, and 3) tightly packed on the discharge vessel 1 in an extrusion manner. The power supply 3 is specifically a high-frequency high-voltage generator, the power of which is determined according to the material, the inner diameter and the wall thickness of the discharge tube 1, is generally set to 5-100 watts, the output frequency is 1.5 kilohertz-1 megahertz, the output voltage is 1-10 kilovolts, and the output frequency and the voltage are adjustable.
Specifically, the sample injection needle 41 includes a needle body and a tip portion, the needle body is provided in a cylindrical structure, and preferably, the surface of the tip portion is engraved with one or more grooves for adsorbing a sample, the grooves may be a plurality of parallel channels or screw channels, and the length, size and shape of the channel portion are arbitrarily selected according to operation or installation requirements. The channel is positioned at the periphery of the tip portion, and can carry the sample so that it does not drip during sampling and introduction.
In the embodiment of the specific cleaning solid sample needle device, the inner diameter of the discharge tube 1 is 2mm, the wall thickness is 1mm, the length is 10-100 mm, the electrode 2 is two sections of conductive layers (a first electrode 21 and a second electrode 22) wrapped on the outer surface of the discharge tube 1, the width of each electrode is 3-10 mm, the interval between the two electrodes is about 20mm, so that electric spark can not be generated between the electrodes 21 and 22 after high-frequency high-voltage application due to the fact that the electric spark can not be generated on the outer surface of the discharge tube due to the fact that the electric spark generated between the two electrodes is related to factors such as the applied voltage and frequency, the wall thickness and the material of the discharge tube, the temperature and the humidity of the environment, and the like, and specific intervals need to be selected through experiments. The first electrode 21 and the second electrode 22 are welded with a wire, and are respectively connected with two output ends of the high-frequency high-voltage power supply 3. When the solid injection needle 41 is extended into the discharge vessel 1, the needle tip passes through the area covered by the first electrode 21 and continues downwards until it approaches the upper edge of the area covered by the second electrode 22 or enters the envelope of the second electrode 22. In practice the needle tip cannot pass through the area enclosed by the second electrode 22, otherwise no discharge occurs. Then the high-frequency high-voltage power supply 3 is connected, the output frequency is regulated to be 1.5 KHz-1 MHz, the voltage is regulated to be about 1-4.5 kilovolts until blue or bluish purple light is emitted from the discharge tube 1, the solid sample injection needle 41 stays in the discharge tube 1 in a discharge state for 0.2-3 seconds, preferably 0.5-1 seconds, at the moment, the sample residual rate of the solid sample injection needle 41 is reduced to be less than 1%, and thus the solid sample injection needle 41 can move upwards to leave the discharge tube 1 to perform the sampling operation of the next sample. In this embodiment, the sample injection needle may be made of a conductive material such as stainless steel, or may be made of a non-conductive material such as ceramic.
In another embodiment of the solid sample injection needle cleaning device, as shown in fig. 2, the inner diameter of the discharge tube 1 is 2mm, the wall thickness is 1mm, the length is 10-100 mm, the electrode 2 is only a section of conductive layer (metal layer or graphite coating) wrapped on the outer surface of the discharge tube 1, in this embodiment, the solid sample injection needle 41 is made of conductive material, so that the electrode 2 and the solid sample injection needle 41 form a pair of blocking discharge electrode pairs, when the solid sample injection needle 41 needs to be cleaned after sample injection is completed, the solid sample injection needle 41 only needs to extend into the upper edge position of the discharge tube 1 close to the electrode 2 or enter the wrapping range of the electrode 2 and not exceed the lower edge position, the output frequency is further adjusted to 1.5 khz-1 mhz, the voltage is adjusted to about 1-4.5 kv, blue or blue-violet light is emitted in the discharge tube 1, the solid sample injection needle 41 stays in the discharge tube 1 in a discharge state for 0.2-3 seconds, and then the next sample can be separated from the discharge tube 1.
When the embodiment of the invention is used for cleaning the solid sample injection needle 41, as the solid sample injection needle 41 carries a very small amount of sample solution, the sample injection needle generally has a few nanoliter to a few microliters, for example, a dip-spray dual-purpose probe, more than 30% of residual signals are usually generated after each sample injection, and when the cleaning device of the embodiment of the invention is used for cleaning, the residual signals of the sample injection needle can be reduced to less than 1% within 1 second.
In a specific embodiment, the needle washing device can be matched with an analysis instrument, such as HPLC, GC, ICP and the like. In some embodiments, the autosampler is provided with a spike-type metal hollow sample injection needle and is connected to a sample-absorbing device, such as a syringe or a sample-absorbing pump, by a capillary tube. The needle washing device of the application is slightly different from that of the solid sample injection needle for the hollow sample injection needle.
Specifically, unlike the structure of the solid sample injection needle 41, typically the sample residue of the hollow sample injection needle 42 is mainly present on the inner surface of the needle, and the needle washing process must allow the plasma to wash the inside of the hollow sample injection needle 42.
Specifically, when the hollow sample injection needle 42 is directly connected with the sample injection needle cylinder in the sample injection process, the needle washing device needs to be additionally provided with a switching device, so that the hollow sample injection needle 42 is connected with the needle cylinder during sample suction and sample injection, and one end (upper end) of the sample injection needle 42, which is communicated with the atmosphere during needle washing, is communicated with the air during needle washing. The switching device can be a three-way valve or a loading and unloading device for the needle head of the hollow sample injection needle 42, namely, the needle head which needs to be contacted with the sample liquid when the hollow sample injection needle 42 sucks and injects samples is tightly connected to the loading and unloading device, the loading and unloading device automatically releases the needle after the needle is inserted into the discharge tube 1 during needle washing, the needle head of the hollow sample injection needle 42 is positioned at the discharge position in the discharge tube, the upper end of the needle head is exposed to the air, and the loading and unloading device can be used for connecting the needle head back to form a tight connection state after the needle washing is finished.
Further, the present invention provides a method for cleaning the hollow sample injection needle 42, firstly, the liquid in the hollow sample injection needle 42 is emptied by a needle cylinder (or sample injection pump), then the hollow sample injection needle 42 is inserted into the discharge tube 1, then the high-frequency high-voltage power supply 3 and the air or oxygen supply are connected, the needle cylinder (or sample injection pump) is used for sucking air, and the plasma generated by the needle tip is sucked into the needle hole to clean the inner surface. In the embodiment of the device for cleaning the hollow sampling needle 42, as shown in fig. 3, the discharge tube 1 is a hollow tube which is sealed and made of insulating material, the inner diameter is 3mm, the wall thickness is 2mm, the length is 10-100 mm, the discharge tube 1 can be made of any solid insulating material which can withstand short time high temperature and keep nonconductive, non-deformation and stable mechanical performance, preferably a quartz tube, a ceramic tube, a glass tube, a carbon fiber tube, a glass fiber tube and the like, at least one needle inlet 11 and one air inlet 12 are arranged on the tube, a sealing cap 6 is arranged at the tube mouth, a through hole is arranged at the top end of the sealing cap 6, a sealing pad 7 is arranged in the sealing cap 6, wherein the sealing pad 7 can be replaced by a cork or a bottle cap with an opening at the top, the sealing pad 7 is tightly sleeved at the upper end of the discharge tube 1, and the opening above the sealing pad 7 allows the hollow sampling needle 42 to be penetrated and pulled out.
Specifically, the needle inlet 11 is provided on the gasket 7 at the opening of one end on the radial axis of the discharge tube 1, and the hollow sample injection needle 42 pierces the gasket 7 into the discharge tube 1. When the hollow injection needle 42 is inserted into the discharge tube 1 through the needle inlet 11, the needle body substantially overlaps the radial axis of the discharge tube 1 and ensures that the needle inlet 11 is air-tight. The gas inlet 12 may be provided at any location of the discharge vessel 1 for introducing gas into the interior of the discharge vessel 1 and for maintaining a seal of the discharge vessel 1. In the drawing, a hollow branch pipe 5 is arranged on the pipe body of the discharge pipe 1, one end of the hollow branch pipe is communicated with the interior of the discharge pipe 1, the other end of the hollow branch pipe is connected with an air source, in other embodiments, a pipe with two open ends can be inserted at the needle inlet 11 in parallel with the needle inlet direction, one end of the pipe is communicated with the interior of the discharge pipe 1, and the other end of the pipe is connected with the air source, wherein the air source can be oxygen or air.
Further, in other embodiments, in the needle washing device of the hollow sample injection needle 42, the discharge tube 1 may be configured as a hollow tube with two open ends, and the gas inlet 12 may be disposed at the other end opposite to the needle inlet 11 for connecting a gas source and inputting a gas.
Specifically, as shown in fig. 3, when the hollow sample injection needle 42 is cleaned, the electrode 2 is formed by two sections of conductive layers wrapped on the outer surface of the discharge tube 1, wherein the widths of the first electrode 21 and the second electrode 22 are 3-10 mm respectively, the interval between the two conductive layers is about 20mm, and each electrode is welded with a wire which is respectively connected with two output ends of the high-frequency high-voltage power supply 3. The hollow branch pipe 5 is connected to a source of pure air or oxygen, and the air supply pressure is regulated to be slightly higher than the ambient air pressure, so that the air flow can flow out from the upper end of the hollow sample injection needle 42, and the plasma can enter the sample injection needle during cleaning conveniently. When the needle pump drives the sample suction and injection of the sample needle, the needle pump is connected to one port of the three-way solenoid valve through a polytetrafluoroethylene capillary tube, the hollow sample needle 42 is connected to the other port, and the third port of the three-way solenoid valve is connected to the atmosphere through a filter (the needle pump and the connecting device are not shown). When the needle is washed, the three-way electromagnetic valve is switched to a state that the hollow sampling needle 42 is communicated with the atmosphere and the needle pump interface is blocked, the hollow sampling needle 42 is penetrated through the sealing gasket 7 to enter the discharge tube 1 until the needle tip of the hollow sampling needle 42 approaches or stretches to a region which is not surrounded by the bottom electrode 2 of the discharge tube 1, at the moment, air or oxygen is introduced and the high-frequency high-voltage power supply 3 is connected, the output frequency is adjusted to 1.5 KHz-1 MHz, the voltage is adjusted to about 1-5 kilovolts until blue-purple luminescence appears in the discharge tube 1, the hollow sampling needle 42 stays in the discharge tube 1 in a discharge state for 0.5-20 seconds, preferably 1-5 seconds, the residual on the hollow sampling needle 42 can be reduced to below 1%, then the three-way electromagnetic valve is switched to a state that the needle pump is communicated with the hollow sampling needle 42 and the interface communicated with the atmosphere is blocked, and the hollow sampling needle 42 moves upwards to leave the discharge tube 1 for the next sampling operation.
In another embodiment of the hollow needle device for cleaning, as shown in fig. 4, the discharge tube 1 is also a hollow tube made of insulating material, the inner diameter is 3mm, the wall thickness is 2mm, the length is 10-100 mm, the discharge tube 1 can be made of any solid insulating material which can withstand short time high temperature and keep nonconductive, non-deforming and stable in mechanical performance, preferably a quartz tube, a ceramic tube, a glass tube, a carbon fiber tube, a glass fiber tube and the like, at least one needle inlet 11 and one air inlet 12 are arranged on the tube, a sealing cap 6 with a central through hole is arranged on the tube opening, and a sealing pad 7 is placed in the sealing cap 6 to seal the through hole and the needle inlet. The electrode 2 is only a conductive layer (metal layer or graphite coating) wrapped on the outer surface of the discharge tube 1, and the hollow sample injection needle 42 is made of conductive material to form another electrode opposite to the conductive layer in this embodiment, so that the electrode 2 and the hollow sample injection needle 42 form a pair of electrodes, when cleaning, the liquid inside the hollow sample injection needle 42 is emptied into the waste liquid by the needle pump, and then the hollow sample injection needle 42 is stretched into the upper edge position of the discharge tube 1 close to the electrode 2 or into the wrapping range of the electrode 2 and does not exceed the lower edge of the electrode 2. The lead of the electrode 2 is connected to one output end of the high-frequency high-voltage power supply 3, the other output end of the high-frequency high-voltage power supply 3 is electrically connected with the hollow sampling needle 42, air or oxygen is introduced and the power supply 3 is connected, the output frequency is regulated to 1.5 KHz-1 MHz, the voltage is regulated to about 1-5 kilovolts and blue-violet light emitted in the discharge tube 1 is seen, meanwhile, a needle pump is used for sucking plasma into the needle for cleaning, the hollow sampling needle 42 stays in the discharge tube 1 in a discharge state for 0.5-20 seconds, preferably 1-5 seconds, the sample residue on the hollow sampling needle 42 can be reduced to below 1%, and then the sample can leave the discharge tube 1 for sampling operation of the next sample.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements, etc. within the principles of the present invention should be included in the scope of the present invention.
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| RU2111071C1 (en) * | 1996-08-16 | 1998-05-20 | Александр Владимирович Гурьянов | Method for cleaning metal surfaces from dielectric deposits |
| DE19907911C2 (en) * | 1999-02-24 | 2003-02-27 | Mag Maschinen Und Appbau Ag Gr | Device and method for the treatment of electrically conductive continuous material |
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