Spray chamber, auxiliary tool for spray chamber, and sample atomization introduction device

Abstract

A spray chamber is provided that enables more effective cleaning.　The spray chamber (AA) has: an end cap (51) that holds a nebulizer (10); a flow path pipe (41) that constitutes a flow path for sample droplets supplied from the nebulizer (10); a sample discharge port (55) that discharges fine droplets from the flow path; a drain discharge port (53) that discharges coarse droplets from the flow path; and a fluid introduction passage that introduces fluid to the flow path pipe (41). The fluid introduction passage has: a fluid supply port; and an annular fluid delivery port that abuts a wall surface of the flow path pipe (41) and follows the circumferential direction of the flow path pipe (41). Fluid that has been supplied to the fluid supply port is sent from the fluid delivery port to the wall surface of the flow path pipe (41).

Description

Spray chamber, auxiliary device for spray chamber, sample atomization and introduction device, and method for operating sample atomization and introduction device

[0001] The present invention relates to a spray chamber, an auxiliary device for the spray chamber, a sample atomization and introduction device, and a method for operating the sample atomization and introduction device. More specifically, the present invention relates to a spray chamber that selects sample droplets based on particle size, an auxiliary device therefor, a sample atomization and introduction device that atomizes a liquid sample and introduces it into an excitation / ionization source, etc., and a method for operating the sample atomization and introduction device.

[0002] Known analytical devices are used to analyze liquid samples using analytical methods such as plasma emission spectrometry, plasma mass spectrometry, atomic absorption spectrometry, atomic fluorescence spectrometry, and liquid chromatography. In these types of analytical devices, the liquid sample is atomized to obtain sample droplets, which are then introduced into an excitation / ionization source. Specifically, the liquid sample is atomized using a nebulizer to obtain sample droplets, and then gravity and inertia are used to cause large sample droplets to collide with and adhere to the inner wall of a spray chamber, thereby removing them, and only the fine sample droplets are introduced into the excitation / ionization source.

[0003] Because sample particles adhere to the inner walls of the spray chamber, a cleaning solution is supplied to the nebulizer after analysis, and the atomized cleaning solution is used to clean the inside of the spray chamber. If the spray chamber is not cleaned sufficiently, the sample remaining in the spray chamber will be mixed into the sample droplets to be analyzed next, resulting in inaccurate analysis results. Furthermore, if sample droplets adhering to the outer wall of the nebulizer and the inner wall of the spray chamber collide with droplets of the cleaning solution or the next sample droplets, gradually increasing in size and flowing into the tip of the nebulizer, the previous sample will be atomized again, resulting in significant errors in the analysis results. This phenomenon is called the memory effect.

[0004] The memory effect is caused by sample residue remaining on the inner walls of the spray chamber. To prevent this, the spray chamber must be cleaned, but introducing cleaning fluid from a nebulizer is inefficient and requires a long cleaning time. In particular, if the sample contains easily volatile components (boron, iodine, mercury, osmium, etc.), these components will evaporate over a long period of time from the sample adhering to the inner walls of the spray chamber, lengthening the cleaning time. Since the next sample cannot be analyzed until cleaning is complete, a long cleaning time reduces the number of analyses per unit time.

[0005] Regarding the cleaning of a spray chamber, Patent Document 1 discloses spraying a cleaning liquid from two nebulizers installed in the spray chamber. Patent Document 2 discloses supplying a cleaning liquid through a pipe extending through the spray chamber to clean the wall surface of the spray chamber. Patent Document 3 discloses introducing a cleaning liquid through a blend gas line connected to the end cap of the spray chamber to clean the inside of the spray chamber.

[0006] JP 2004-286604 JP 9-239298 JP 10-188877

[0007] However, in the method of Patent Document 1, the spray chamber is cleaned with atomized cleaning liquid, which limits the improvement of cleaning efficiency. Furthermore, the introduction of cleaning liquid droplets into the plasma torch places an excessive load on the plasma, reducing excitation and ionization efficiencies. Furthermore, the amount of interfering components, such as polyatomic ions, originating from the cleaning liquid increases.

[0008] Furthermore, in the methods of Patent Documents 2 and 3, the area in which the cleaning liquid flows is limited to the periphery of the opening of the pipe and the downstream portion thereof, so the entire spray chamber cannot be cleaned.

[0009] In view of the above circumstances, the present invention aims to provide a spray chamber that can be cleaned more effectively, an auxiliary tool therefor, a sample atomization and introduction device equipped with the spray chamber, and a method for operating the sample atomization and introduction device.

[0010] A first aspect of the spray chamber includes an end cap for holding a nebulizer, a flow path conduit that forms part or all of a flow path for sample droplets supplied from the nebulizer, a sample outlet for discharging fine droplets from the flow path, a drain outlet for discharging coarse droplets from the flow path, and a liquid inlet conduit for introducing liquid into the flow path conduit, the liquid inlet conduit having a liquid supply port and an annular liquid outlet that contacts a wall surface of the flow path conduit and extends circumferentially along the flow path conduit, the liquid supplied to the liquid supply port being discharged from the liquid outlet onto the wall surface. A second aspect of the spray chamber is the first aspect, characterized in that the liquid discharged from the liquid outlet forms a liquid film flow on the wall surface and is discharged from the drain outlet. A third aspect of the spray chamber is the first or second aspect, characterized in that the liquid inlet conduit has a liquid dispersion section that disperses the liquid supplied to the liquid supply port and guides it to the liquid outlet. A fourth aspect of the spray chamber is the third aspect, characterized in that the liquid dispersion section is an annular passage formed along the circumferential direction of the flow path pipe. A fifth aspect of the spray chamber is the third aspect, characterized in that the liquid dispersion section is a liquid storage section that temporarily stores the liquid. A sixth aspect of the spray chamber is the fifth aspect, characterized in that the liquid introduction passage has an impregnated body that is filled in the liquid storage section and into which the liquid is soaked. A seventh aspect of the spray chamber is the third aspect, characterized in that the liquid dispersion section comprises a plurality of dispersion passages connecting the liquid supply port and multiple locations of the liquid delivery port. A eighth aspect of the spray chamber is any of the first to seventh aspects, characterized in that the liquid delivery port is a completely connected annular opening. A ninth aspect of the spray chamber is any of the first to seventh aspects, characterized in that the liquid delivery port comprises a plurality of small openings arranged annularly. A tenth aspect of the spray chamber is any of the first to seventh aspects, characterized in that a partial circumferential area of ​​the liquid delivery port is closed.An eleventh aspect of the spray chamber is any of the first to tenth aspects, characterized in that the liquid introduction path has an auxiliary wall disposed across a gap from the wall surface and forming a liquid film formation path between the wall surface and the auxiliary wall, and the outlet side edge of the auxiliary wall has a wedge-shaped cross section with an acute angle on the liquid-contacting side.A twelfth aspect of the spray chamber is any of the first to eleventh aspects, characterized in that it has a liquid film flow guide surrounding the sample outlet and inhibiting the inflow of the liquid.A thirteenth aspect of the spray chamber is any of the first to twelfth aspects, characterized in that it has a liquid film flow guide surrounding the end cap and inhibiting the inflow of the liquid. A fourteenth aspect of the spray chamber auxiliary device is an auxiliary device attached to a flow path tube that constitutes part or all of a flow path for sample droplets supplied from a nebulizer, and includes a liquid introduction path for introducing liquid into the flow path tube, the liquid introduction path having a liquid supply port and an annular liquid outlet that, when attached to the flow path tube, contacts the wall surface of the flow path tube and extends circumferentially around the flow path tube, and the liquid supplied to the liquid supply port is delivered to the wall surface from the liquid outlet. A fifteenth aspect of the sample atomization introduction device is characterized by including a spray chamber to which any of the spray chambers of the first to thirteenth aspects or the spray chamber auxiliary device of the fourteenth aspect is attached, and a nebulizer attached to the spray chamber. A sixteenth aspect of the sample atomization introduction device is the fifteenth aspect, further including a sample supply source that supplies a liquid sample to the nebulizer, and a liquid supply source that supplies a cleaning liquid to the liquid supply port, and the liquid supply source supplies the cleaning liquid to the liquid supply port at least while the sample supply source is supplying the liquid sample to the nebulizer. A seventeenth aspect of the sample atomization introduction device is the sixteenth aspect, characterized in that the cleaning liquid is cooled. A eighteenth aspect of the sample atomization introduction device is the fifteenth aspect, characterized in that it includes a sample supply source that supplies a liquid sample to the nebulizer and a liquid supply source that supplies a cleaning liquid to the liquid supply port, and that after the supply of the liquid sample from the sample supply source to the nebulizer is completed, the cleaning liquid is supplied from the liquid supply source to the liquid supply port.A 19th aspect of the sample nebulization introduction device is characterized in that the cleaning liquid contains a surfactant in any of the 16th to 18th aspects. A 20th aspect of the sample nebulization introduction device is characterized in that the 15th aspect includes a sample supply source that supplies a liquid sample to the nebulizer and a liquid supply source that supplies a reaction liquid to the liquid supply port, and the sample supply source supplies the liquid sample to the nebulizer while the liquid supply source simultaneously supplies the reaction liquid to the liquid supply port, causing the sample droplets and the reaction liquid to react in the spray chamber. A 21st aspect of the sample nebulization introduction device is characterized in that the reaction liquid is heated in the 20th aspect. A 22nd aspect of the method for operating the sample nebulization introduction device is characterized in that a cleaning liquid is supplied to the liquid supply port at least while the liquid sample is being supplied to the nebulizer. A 23rd aspect of the method for operating the sample nebulization introduction device is characterized in that the cleaning liquid is cooled in the 22nd aspect. A 24th aspect of the method for operating a sample nebulization introduction device is the 15th aspect of the method, characterized in that a cleaning solution is supplied to the liquid supply port after the supply of the liquid sample to the nebulizer is completed. A 25th aspect of the method for operating a sample nebulization introduction device is any of the 22nd to 24th aspects, characterized in that the cleaning solution contains a surfactant. A 26th aspect of the method for operating a sample nebulization introduction device is the 15th aspect of the method, characterized in that a reaction solution is supplied to the liquid supply port simultaneously with the supply of the liquid sample to the nebulizer, and the sample droplets and the reaction solution are reacted in the spray chamber. A 27th aspect of the method for operating a sample nebulization introduction device is the 26th aspect of the method, characterized in that the reaction solution is heated.

[0011] According to the first and second aspects, when a cleaning liquid is supplied to the liquid supply port, a liquid film flow of the cleaning liquid is formed on the wall surface of the flow path tube. Large droplets are captured by the liquid film flow, making it difficult for the sample to remain on the wall surface of the flow path tube. Furthermore, the liquid film flow can wash away a wide area of ​​the wall surface of the flow path tube. This allows for effective cleaning of the flow path tube. According to the third aspect, the liquid is dispersed in the liquid dispersion section, allowing the liquid to be uniformly discharged from the entire area of ​​the annular liquid discharge port. According to the fourth aspect, the liquid is dispersed by flowing along the annular path. According to the fifth aspect, the liquid is dispersed by temporarily storing in the liquid storage section. According to the sixth aspect, the liquid permeates the impregnated body, making it easier to disperse the liquid. According to the seventh aspect, the liquid is dispersed by flowing through multiple dispersion paths. According to the eighth aspect, the liquid can be uniformly discharged circumferentially around the flow path tube. According to the ninth aspect, the liquid can be discharged at high speed from the liquid discharge port, thereby increasing the area of ​​the wall surface of the flow path tube that is covered by the liquid film flow. According to the tenth aspect, since the liquid film flow is discharged only from the open portion of the liquid outlet, a liquid film flow can be formed in a concentrated manner in a specific area, such as an area on the wall surface of the flow path where sample droplets are likely to adhere. According to the eleventh aspect, since the edge of the outlet side of the auxiliary wall is wedge-shaped, liquid is less likely to adhere to the edge, and the liquid is prevented from falling as droplets. Therefore, a liquid film flow can be smoothly discharged. According to the twelfth aspect, the liquid film flow guide can suppress the inflow of liquid into the sample outlet. According to the thirteenth aspect, the liquid film flow guide can suppress the inflow of liquid into the end cap and the nebulizer. According to the fourteenth aspect, by attaching an auxiliary tool, an existing spray chamber can be configured to form a liquid film flow on the wall surface of the flow path. According to the fifteenth aspect, the spray chamber can be effectively cleaned. According to the sixteenth aspect, since large droplets supplied from the nebulizer are captured by the liquid film flow of the cleaning liquid formed on the wall surface of the flow path, the sample is less likely to remain on the wall surface of the flow path. According to the seventeenth aspect, the amount of water vapor caused by sample droplets is reduced, thereby improving the excitation efficiency and ionization efficiency of the analyzer. Also, it is possible to reduce interfering components caused by water. According to the eighteenth aspect, the sample adhering to the wall surface of the flow path tube can be washed away by the liquid film flow of the cleaning liquid.According to the 19th aspect, even when an organic solvent sample is used as the liquid sample, the organic solvent adhering to the wall surface of the flow path tube can be easily washed away. According to the 20th aspect, the reaction liquid forms a liquid film flow inside the spray chamber and spreads over a wide area, thereby improving the reaction rate and vaporization rate of the sample. According to the 21st aspect, the reaction temperature is increased, thereby accelerating the reaction between the sample droplets and the reaction liquid. According to the 22nd aspect, coarse droplets supplied from the nebulizer are captured by the liquid film flow of the cleaning liquid formed on the wall surface of the flow path tube, making it difficult for the sample to adhere to the wall surface of the flow path tube. According to the 23rd aspect, the amount of water vapor caused by the sample droplets is reduced, thereby improving the excitation efficiency and ionization efficiency of the analyzer. Furthermore, interfering components caused by water can be reduced. According to the 24th aspect, the sample adhering to the wall surface of the flow path tube can be washed away by the liquid film flow of the cleaning liquid. According to the 25th aspect, even when an organic solvent sample is used as the liquid sample, the organic solvent adhering to the wall surface of the flow path tube can be easily washed away. According to the 26th aspect, the reaction liquid forms a liquid film flow inside the spray chamber and spreads over a wide area, thereby improving the reaction rate and vaporization rate of the sample. According to the twenty-seventh aspect, the reaction temperature is increased, and therefore the reaction between the sample droplets and the reaction liquid is accelerated.

[0012] 1. An explanatory diagram of a sample atomization and introduction device of a first embodiment. A vertically cut end view of a spray chamber of a first embodiment. An enlarged view of the periphery of the holder in FIG. 2. A cross-sectional view taken along line IV-IV in FIG. 2. A horizontal cross-sectional view of a spray chamber of another example. An vertically cut end view of a spray chamber of a second embodiment. An enlarged view of the periphery of the first and second auxiliary walls in FIG. 6. An vertically cut end view of a spray chamber of a third embodiment. A cross-sectional view taken along line IX-IX in FIG. 8. An vertically cut end view of a spray chamber of a fourth embodiment. An vertically cut end view of a spray chamber of a fifth embodiment. An vertically cut end view of a spray chamber of a sixth embodiment. A cross-sectional view taken along line XIII-XIII in FIG. 12. An vertically cut end view of a spray chamber of a seventh embodiment. A cross-sectional view taken along line XV-XV in FIG. 14. Figure (A) is a cross-sectional view taken along line XVIa-XVIa in FIG. 15. Figure (B) is a cross-sectional view of an end cap and an end cap holding tube of another example. 21。(B) is a cross-sectional view taken along line XXIIIa in FIG. 21. FIG. 21(B) is a cross-sectional view taken along line XXIIIb in FIG. 21. FIG. 21(A) is a cross-sectional view taken along line XXIVa in FIG. 21. FIG. 21(B) is a cross-sectional view taken along line XXIVb in FIG. 21. FIG. 21(A) is a side view of a liquid film forming channel 64. FIG. 21(B) is a side view of a liquid film forming channel 64 in another example. FIG. 21(C) is a side view of a liquid film forming channel 64 in yet another example. FIG. 21(C) is a side view of a liquid film forming channel 64 in yet another example. FIG. 21(B) is a cross-sectional view taken along line XXIVb in FIG. 21. Figure (A) is a vertically cut end view of the periphery of an impregnated body of another example. Figure (B) is a vertically cut end view of the periphery of an impregnated body of yet another example. Figure (C) is a vertically cut end view of the periphery of an impregnated body of yet another example. Figure (A) is a vertically cut end view of the periphery of an impregnated body of an eleventh embodiment.Figure (B) is a cross-sectional view taken along the line b-b in Figure (A). Figure (A) is an end view of a vertical section of a spray chamber of another example. Figure (B) is a cross-sectional view taken along the line b-b in Figure (A). Figure (A) is an end view of a vertical section of a spray chamber of yet another example. Figure (B) is a cross-sectional view taken along the line b-b in Figure (A). Figure (A) is an end view of a vertical section of a spray chamber of a twelfth embodiment. Figure (B) is an enlarged cross-sectional view taken along the line b in Figure (A). An end view of a vertical section of a spray chamber of another example. An end view of a vertical section of a spray chamber of yet another example.

[0013] Next, embodiments of the present invention will be described with reference to the drawings. [First Embodiment] (Sample Atomization and Introduction Apparatus) As shown in FIG. 1, a sample atomization and introduction apparatus AT according to a first embodiment of the present invention is a component of an analytical apparatus for analyzing a liquid sample by an analytical method such as plasma optical emission spectrometry, plasma mass spectrometry, atomic absorption spectrometry, atomic fluorescence spectrometry, or liquid chromatography. The sample atomization and introduction apparatus AT atomizes a liquid sample to generate sample droplets, and then introduces the sample droplets after particle size sorting into an excitation / ionization source (EI) within the analytical apparatus. For example, the excitation / ionization source (EI) is plasma in an ICP analyzer, which is generated by a plasma torch. In liquid chromatography, the sample droplets are introduced into a light scattering detector. Such detectors are also included in the excitation / ionization source (EI).

[0014] The sample atomization and introduction device AT has a nebulizer 10 that atomizes a liquid sample and a spray chamber AA that selects sample droplets by particle size. The nebulizer 10 is attached to the spray chamber AA and supplies sample droplets into the spray chamber AA.

[0015] A sample supply source 20 that supplies a liquid sample is connected to the nebulizer 10. The sample supply source 20 is composed of, for example, a container 21 that stores the liquid sample, a flexible tube 22 that connects the nebulizer 10 and the container 21, and a peristaltic pump 23 provided in the middle of the tube 22. The liquid sample is supplied to the nebulizer 10 by operation of the sample supply source 20.

[0016] Three liquid supply sources, namely, first, second, and third liquid supply sources 30A, 30B, and 30C, are connected to the spray chamber AA. The first liquid supply source 30A comprises a container 31A for storing a liquid such as a cleaning liquid, a flexible tube 32A connecting the spray chamber AA to the container 31A, and a peristaltic pump 33A disposed midway along the tube 32A. The second and third liquid supply sources 30B and 30C may have the same configuration as the first liquid supply source 30A. Liquid such as a cleaning liquid is supplied to the spray chamber AA by the operation of each liquid supply source 30A, 30B, and 30C.

[0017] The sample supply source 20 and the first, second, and third liquid supply sources 30A, 30B, and 30C can each be controlled by a control device 25. The control device 25 can control the flow rate and supply / stop of liquids such as the liquid sample and cleaning solution. This control can be achieved, for example, by controlling the operating speed and start / stop of the peristaltic pumps 23 and 33A. The liquid supply sources may also be manually operated sources such as syringes that supply liquid.

[0018] (Spray Chamber) Next, the spray chamber AA of this embodiment will be described. As shown in Figure 2, the spray chamber AA is a so-called Scott-type spray chamber. The spray chamber AA has an inner pipe 41 and an outer pipe 42. Both the inner pipe 41 and the outer pipe 42 are circular pipes. The inner pipe 41 has a smaller diameter than the outer pipe 42 and is disposed inside the outer pipe 42. The inner pipe 41 and the outer pipe 42 are disposed coaxially to form a double pipe.

[0019] An end cap 51 is attached to the upper end of the inner tube 41. The end cap 51 holds the nebulizer 10. The nebulizer 10 may be of any type, such as a coaxial type, a crossflow type, or a Babington type. The nebulizer 10 shown in the figure is a coaxial type. A tube 22 of a sample supply source 20 is connected to the inner tube of the nebulizer 10, and a liquid sample is introduced into the tube. A carrier gas is introduced into the outer tube of the nebulizer 10. The liquid sample supplied to the nebulizer 10 is atomized by the carrier gas, and the sample droplets are sprayed into the interior of the inner tube 41. The sample droplets are sprayed from the upper end of the inner tube 41 along the central axis of the inner tube 41.

[0020] A gap is formed between the outer peripheral surface of nebulizer 10 and the inner peripheral surface of end cap 51. End cap 51 also has sheath gas supply port 52 that communicates with the gap. When sheath gas is supplied from a tube connected to sheath gas supply port 52, the sheath gas is sprayed from the outer periphery of nebulizer 10. The sheath gas can prevent sample droplets from adhering to the tip of nebulizer 10.

[0021] The lower end of the inner tube 41 is at least partially open, and the internal space of the inner tube 41 communicates with the internal space of the outer tube 42. The outer tube 42 is a tube with a bottom. A drain outlet 53 is provided at the bottom of the outer tube 42. The upper part of the outer tube 42 is closed by a holder 54. The holder 54 has a sample outlet 55 that communicates between the inside and outside of the outer tube 42.

[0022] At least a portion of the sample droplets supplied from the nebulizer 10 flows from the upper end to the lower end within the internal space of the inner tube 41, then flows from the lower end to the upper end within the space between the inner tube 41 and the outer tube 42, and is discharged from the sample outlet 55. In this manner, the inner tube 41 and the outer tube 42 form a flow path for the sample droplets. The inner tube 41 and the outer tube 42 each correspond to a "flow path tube" as defined in the claims.

[0023] Here, "flow path tube" refers to a tube that constitutes part or all of the flow path of the sample droplets. The spray chamber AA of this embodiment has multiple (two) flow path tubes. The two flow path tubes (inner tube 41 and outer tube 42) each constitute part of the flow path of the sample droplets. It is also possible to consider a spray chamber with a single-tube structure that does not have an inner tube 41 and constitutes the flow path only with the outer tube 42. In this case, the flow path tube (outer tube 42) constitutes the entire flow path of the sample droplets.

[0024] Among the sample droplets supplied from the nebulizer 10, droplets with a relatively large particle size collide with and adhere to the wall surfaces of the inner tube 41 and the outer tube 42 as they flow along the flow path, becoming drain and being discharged from the drain outlet 53. Of the sample droplets, only droplets with a relatively small particle size are discharged from the sample outlet 55. In this specification, the sample droplets discharged from the sample outlet 55 are referred to as "fine droplets," and the sample droplets discharged from the drain outlet 53 are referred to as "coarse droplets." The average particle size of the fine droplets is smaller than the average particle size of the coarse droplets. However, the particle size of some of the fine droplets may be larger than the particle size of some of the coarse droplets.

[0025] The fine droplets discharged from the sample outlet 55 are introduced into the EI, such as the excitation / ionization source, via piping (FIG. 1). On the other hand, the drain discharged from the drain outlet 53 is collected in a container or the like.

[0026] 3, the spray chamber AA has three liquid introduction paths, namely, first, second and third liquid introduction paths 60A, 60B and 60C. Each of the liquid introduction paths 60A, 60B and 60C is a flow path that introduces a liquid such as a cleaning liquid supplied from each of the liquid supply sources 30A, 30B and 30C into the inner tube 41 or the outer tube 42.

[0027] The first liquid introduction path 60A has a first liquid supply port 61A and a first liquid delivery port 62A. The liquid supplied to the first liquid supply port 61A is delivered from the first liquid delivery port 62A. The first liquid supply port 61A is formed in the holder 54. A tube 32A of a first liquid supply source 30A is connected to the first liquid supply port 61A.

[0028] 3 and 4, a first annular passage 63A is formed at the joint between the end cap 51 and the holder 54. The first annular passage 63A is an annular flow path that runs along the circumferential direction of the inner pipe 41. The first liquid supply port 61A is in communication with the first annular passage 63A.

[0029] A first liquid film forming passage 64A is formed between the lower outer peripheral surface of the end cap 51 and the inner wall surface 41i of the inner pipe 41 (hereinafter referred to as the inner pipe inner wall surface 41i). The first liquid film forming passage 64A is a cylindrical flow path formed along the first annular passage 63A. The upper edge of the first liquid film forming passage 64A communicates with the first annular passage 63A, and the lower edge opens along the inner pipe inner wall surface 41i. The opening at the lower edge of the first liquid film forming passage 64A is a first liquid delivery outlet 62A. The first liquid delivery outlet 62A is an annular opening that contacts the inner pipe inner wall surface 41i and follows the circumferential direction of the inner pipe 41.

[0030] The outer peripheral surface of the lower part of the end cap 51 forms the side wall of the first annular passage 63A and extends downward to face the inner pipe inner wall surface 41i. The portion of the outer peripheral surface of the end cap 51 facing the inner pipe inner wall surface 41i is referred to as the first auxiliary wall 65A. The first auxiliary wall 65A is disposed with a gap between it and the inner pipe inner wall surface 41i, and forms a first liquid film formation passage 64A between itself and the inner pipe inner wall surface 41i.

[0031] When cleaning liquid is supplied from the tube 32A of the first liquid supply source 30A to the first liquid supply port 61A, the cleaning liquid is supplied to the first annular passage 63A. The cleaning liquid flows circumferentially along the first annular passage 63A, then flows into the first liquid film forming passage 64A and is discharged from the first liquid discharge port 62A. The cleaning liquid in the first annular passage 63A forms a film in the first liquid film forming passage 64A and is discharged onto the inner pipe inner wall surface 41i. The first liquid discharge port 62A is an annular opening that runs along the circumferential direction of the inner pipe 41 and is located at the upper end of the inner pipe 41. Therefore, the cleaning liquid is uniformly discharged along the circumferential direction of the inner pipe inner wall surface 41i, forming a liquid film flow that covers almost the entire surface. The cleaning liquid that flows down the inner pipe inner wall surface 41i is discharged from the drain outlet 53 (FIG. 2).

[0032] The opening width of the first liquid delivery port 62A (the distance between the first auxiliary wall 65A and the inner pipe inner wall surface 41i) is not particularly limited, but is preferably 0.01 to 3.0 mm, and more preferably 0.05 to 0.5 mm. This opening width allows for the formation of a sufficiently thin liquid film flow without excessive liquid delivery resistance. Furthermore, the end cap 51 and other components can be easily fabricated.

[0033] As shown in FIG. 4 , the first liquid supply port 61A may be connected to the first annular passage 63A in a normal direction. Alternatively, as shown in FIG. 5 , the first liquid supply port 61A may be connected to the first annular passage 63A in a tangential direction. The angle at which the first liquid supply port 61A is connected to the first annular passage 63A may be intermediate between the normal direction and the tangential direction. When the first liquid supply port 61A is connected to the first annular passage 63A in a tangential direction, the cleaning liquid supplied from the first liquid supply port 61A to the first annular passage 63A easily flows in the circumferential direction (counterclockwise in the example shown in FIG. 5 ) along the first annular passage 63A. This facilitates the cleaning liquid to spread throughout the entire circumference of the inner tube 41.

[0034] The first annular passage 63A is one form of the "liquid dispersion section" described in the claims. Here, the "liquid dispersion section" refers to a section that disperses the liquid supplied to the liquid supply port and guides it to the liquid discharge port. The liquid supplied to the liquid supply port is dispersed in the liquid dispersion section, allowing the liquid to be discharged evenly from the entire area of ​​the annular liquid discharge port. In other words, a specific water path is formed between the liquid supply port and a partial area of ​​the liquid discharge port, preventing the liquid from flowing unevenly to a partial area of ​​the liquid discharge port. The first annular passage 63A disperses the liquid by flowing it in a circular manner. This allows the first annular passage 63A to function as a liquid dispersion section.

[0035] As shown in FIG. 3 , the second liquid introduction path 60B has a second liquid supply port 61B and a second liquid discharge port 62B. The second liquid supply port 61B is formed in the holder 54. A tube 32B of the second liquid supply source 30B is connected to the second liquid supply port 61B. A second annular path 63B and a second liquid film forming path 64B are formed between the holder 54 and the outer wall surface 41o of the inner pipe 41 (hereinafter referred to as the inner pipe outer wall surface 41o). The second annular path 63B is an annular flow path along the circumferential direction of the inner pipe 41. The second liquid film forming path 64B is a cylindrical flow path formed along the second annular path 63B. A portion of the inner circumferential surface of the holder 54 forms a second auxiliary wall 65B, which is disposed with a gap between it and the inner pipe outer wall surface 41o. The second liquid film forming path 64B is formed between the second auxiliary wall 65B and the inner pipe outer wall surface 41o. The second liquid supply port 61B is connected to the second annular passage 63B. An opening at the lower edge of the second liquid film formation passage 64B is the second liquid delivery port 62B. The second liquid delivery port 62B is an annular opening that contacts the inner pipe outer wall surface 41o and extends in the circumferential direction of the inner pipe 41.

[0036] When cleaning liquid is supplied to the second liquid supply port 61B, the cleaning liquid flows circumferentially along the second annular path 63B, then flows into the second liquid film forming path 64B, and is delivered from the second liquid delivery port 62B in the form of a film onto the inner pipe outer wall surface 41o. The cleaning liquid forms a liquid film flow that covers almost the entire inner pipe outer wall surface 41o. The cleaning liquid that flows down along the inner pipe outer wall surface 41o is discharged from the drain discharge port 53.

[0037] The third liquid introduction path 60C has a third liquid supply port 61C and a third liquid discharge port 62C. The third liquid supply port 61C is formed in the holder 54. A tube 32C of the third liquid supply source 30C is connected to the third liquid supply port 61C. A third annular path 63C and a third liquid film formation path 64C are formed between the holder 54 and the outer wall surface 42o of the outer tube 42 (hereinafter referred to as the outer tube outer wall surface 42o). The third annular path 63C is an annular flow path along the circumferential direction of the outer tube 42. The third liquid film formation path 64C is a cylindrical flow path formed along the third annular path 63C. A portion of the inner circumferential surface of the holder 54 forms a third auxiliary wall 65C, which is disposed across a gap from the outer tube outer wall surface 42o. The third liquid film formation path 64C is formed between the third auxiliary wall 65C and the outer tube outer wall surface 42o. The third liquid supply port 61C communicates with the third annular passage 63C. The third liquid film formation passage 64C has a lower edge that communicates with the third annular passage 63C and an upper edge that serves as a third liquid delivery port 62C that opens along the upper edge of the outer pipe 42. Therefore, the third liquid delivery port 62C is in contact with the outer wall surface 42o of the outer pipe and is an annular opening that follows the circumferential direction of the outer pipe 42.

[0038] When cleaning liquid is supplied to the third liquid supply port 61C, the cleaning liquid flows circumferentially along the third annular path 63C and then rises within the third liquid film forming path 64C. The cleaning liquid passes over the upper edge of the outer pipe 42 from the third liquid delivery port 62C and is delivered in the form of a film onto the inner wall surface 42i of the outer pipe 42 (hereinafter referred to as the outer pipe inner wall surface 42i). Therefore, the cleaning liquid forms a liquid film flow that covers almost the entire outer pipe inner wall surface 42i. The cleaning liquid that flows down along the outer pipe inner wall surface 42i is discharged from the drain outlet 53.

[0039] In this embodiment, the third liquid film forming path 64C is configured to first raise the cleaning liquid and then allow it to flow down, but similar to the first and second liquid film forming paths 64A and 64B, it may also be configured to allow the cleaning liquid to flow down without rising.

[0040] Furthermore, the spray chamber AA of this embodiment is configured to form a liquid film flow on all of its internal wall surfaces, i.e., the inner pipe inner wall surface 41i, the inner pipe outer wall surface 41o, and the outer pipe inner wall surface 42i, but it may also be configured to form a liquid film flow on only some of these surfaces.

[0041] The inner pipe 41 and the outer pipe 42 are not limited to circular pipes, but may be of other shapes, such as rectangular pipes. The shapes of the first annular passage 63A, the first liquid film formation passage 64A, and the first liquid delivery port 62A depend on the cross-sectional shape of the inner pipe 41. For example, if the inner pipe 41 is a rectangular pipe, the first annular passage 63A, the first liquid film formation passage 64A, and the first liquid delivery port 62A will be rectangular ring-shaped. The same applies to the second and third annular passages 63B and 63C, the second and third liquid film formation passages 64B and 64C, and the second and third liquid delivery ports 62B and 62C.

[0042] In this embodiment, the cleaning liquid flows down along the wall surfaces 41i, 41o, and 42i mainly due to the action of gravity. In order to form a liquid film flow that covers the entire wall surfaces 41i, 41o, and 42i, it is preferable to arrange the spray chamber AA vertically with the end cap 51 at the top and the drain outlet 53 at the bottom. Specifically, it is preferable that the angle of the central axis of the spray chamber AA (the central axis of the inner pipe 41 and the outer pipe 42) with respect to the horizontal plane be 75 to 90 degrees.

[0043] However, the liquid film flow can easily cover the entire wall surfaces 41i, 41o, 42i by increasing the speed of the cleaning liquid or by shortening the inner pipe 41 and the outer pipe 42. In such cases, the spray chamber AA may be laid down (the angle of the central axis relative to the horizontal plane may be less than 75°).

[0044] (Operation Method) Next, the operation method of the sample atomization and introduction device AT will be described. The operation method described below may be performed automatically by the control device 25 provided in the sample atomization and introduction device AT, or may be performed manually by an operator.

[0045] (1) Cleaning As shown in Figure 1, when analyzing a sample using an analytical device, a sample supply source 20 is operated to supply a liquid sample to a nebulizer 10. The liquid sample is atomized by the nebulizer 10 to form sample droplets. The sample droplets are sorted in a spray chamber AA, and only the fine droplets are introduced into an excitation / ionization source, such as EI.

[0046] The first, second, and third liquid supply sources 30A, 30B, and 30C supply cleaning liquid to the first, second, and third liquid supply ports 61A, 61B, and 61C of the spray chamber AA at least while the sample supply source 20 is supplying the liquid sample to the nebulizer 10, i.e., while the sample is being analyzed by the analyzer. In addition to pure water, an acid solution such as nitric acid can be used as the cleaning liquid.

[0047] When cleaning liquid is supplied to the first, second, and third liquid supply ports 61A, 61B, and 61C, a liquid film flow of the cleaning liquid is formed on the wall surfaces 41i, 41o, and 42i of the spray chamber AA. In conventional spray chambers, coarse droplets collide with and adhere to the dry wall surfaces, making it easy for the sample to remain on the wall surfaces. In contrast, in this embodiment, coarse droplets are captured in the liquid film flow formed on the wall surfaces 41i, 41o, and 42i, making it difficult for the sample to remain on the wall surfaces 41i, 41o, and 42i. The cleaning liquid that has captured the coarse droplets is discharged from the drain outlet 53.

[0048] In addition, the liquid film flow can wash a wide range of the wall surfaces 41i, 41o, and 42i. Therefore, even if large droplets adhere to the wall surfaces 41i, 41o, and 42i, they are quickly washed away. In this way, the spray chamber AA of this embodiment can effectively clean the inner tube 41 and the outer tube 42.

[0049] Furthermore, because the cleaning liquid is not atomized, almost the entire amount is discharged from the drain outlet 53. Because droplets of the cleaning liquid are not introduced into the excitation / ionization source, the excitation efficiency and ionization efficiency are not reduced. There is also no increase in interfering components, such as polyatomic ions and oxides of the target element, that are caused by the cleaning liquid.

[0050] In this embodiment, the large droplets collide with the liquid film flow of the cleaning liquid. This collision between water and water creates a strong hydrophilic interaction, so the large droplets can be removed more efficiently than from a dry wall surface. This allows the spray chamber AA to be made smaller by shortening the inner tube 41 and outer tube 42, for example.

[0051] After the supply of the liquid sample from the sample supply source 20 to the nebulizer 10 has been completed, i.e., after the analysis of the sample in the analyzer has been completed, cleaning liquid may be supplied from the first, second, and third liquid supply sources 30A, 30B, and 30C to the first, second, and third liquid supply ports 61A, 61B, and 61C. Cleaning liquid may be supplied both during the analysis period in the analyzer and after the end of the analysis period, or cleaning liquid may not be supplied during the analysis period but may be supplied after the end of the analysis period. Note that cleaning liquid may be supplied from a syringe after the end of the analysis period to perform cleaning all at once.

[0052] Even in this case, the sample adhering to the wall surfaces 41i, 41o, and 42i can be washed away by the liquid film flow of the cleaning liquid. If the cleaning liquid is supplied only after the end of the analysis period, the amount of cleaning liquid used can be reduced. In addition, the operating time of the pump that supplies the cleaning liquid is shortened, which saves energy and extends the life of the device.

[0053] A cooled cleaning liquid may be supplied to the spray chamber AA. The cleaning liquid may be cooled to a temperature lower than room temperature (25°C). For example, when pure water is used as the cleaning liquid, the cleaning liquid cooled to 2 to 10°C may be supplied to the spray chamber AA. ２ A freezing point depressant such as ethylene glycol may be added to the cleaning solution so that the cleaning solution will not freeze even if it is cooled to 0°C or below, for example, -20°C, and supplied to the spray chamber AA.

[0054] Supplying cooled cleaning fluid to the spray chamber AA reduces the amount of saturated water vapor, thereby reducing the amount of water vapor caused by the sample droplets and cleaning fluid. This reduces the amount of water vapor introduced into the EI excitation / ionization source, improving excitation and ionization efficiency. It also reduces interfering components caused by water.

[0055] It is possible to cool conventional spray chambers from the outside using a Peltier element, cooling water, etc. However, because the interior of the spray chamber is cooled by heat conduction, it is difficult to cool the inner pipe of a spray chamber with a double-pipe structure. In contrast, in this embodiment, a liquid film flow of cooled cleaning liquid is formed on the inner wall surface 41i and outer wall surface 41o of the inner pipe 41, making it easy to cool the inner pipe 41.

[0056] Liquid samples are usually aqueous solutions, but may contain organic solvents such as gasoline or toluene. When analyzing such organic solvent samples, a cleaning solution containing a surfactant may be used. Examples of surfactants that can be used include RBS-25 manufactured by Sigma-Aldrich and Triton X manufactured by Dow Chemical Company.

[0057] Even if organic solvents adhere to the wall surfaces 41i, 41o, and 42i of the spray chamber AA, they can be easily cleaned off with a cleaning solution containing a surfactant. Furthermore, because the amount of organic solvent vapor introduced into the EI (excitation / ionization source) is reduced, excitation efficiency and ionization efficiency are not reduced, and interfering components caused by the organic solvent can be reduced. This effect is further enhanced by cooling the cleaning solution containing a surfactant.

[0058] When switching from an organic solvent sample to an aqueous solution sample, or vice versa, conventional spray chambers require a longer cleaning time or require the spray chamber to be removed from the analyzer for cleaning. In contrast, the spray chamber AA of this embodiment allows for the exchange of organic solvent samples and aqueous solutions with a short cleaning time. This allows for a greater number of analyses per unit time.

[0059] Furthermore, the surfactant reduces the surface tension of water, which makes it easier for the cleaning liquid to spread over the wall surfaces 41i, 41o, and 42i, and to form a thin liquid film flow that covers the entire wall surfaces 41i, 41o, and 42i.

[0060] (2) Reaction A reaction liquid may be supplied to the spray chamber AA instead of a cleaning liquid. If a reaction liquid is stored in the containers of the first, second, and third liquid supply sources 30A, 30B, and 30C, the reaction liquid can be supplied. A liquid that undergoes a chemical reaction with the sample is selected as the reaction liquid.

[0061] A liquid sample is supplied from sample supply source 20 to nebulizer 10. At the same time, a reaction liquid is supplied from first liquid supply source 30A to first liquid supply port 61A. Then, sample droplets sprayed from nebulizer 10 come into contact with the liquid film flow of the reaction liquid formed on inner tube inner wall surface 41i, and the sample droplets and reaction liquid react within spray chamber AA.

[0062] To react the sample droplets with the reaction solution, the liquid sample and the reaction solution may be supplied to the spray chamber AA simultaneously. Here, "simultaneously" means that there is a period during which both the liquid sample and the reaction solution are supplied to the spray chamber AA. The timing of the start and end of supply of the liquid sample and the reaction solution may differ. Typically, the supply of the liquid sample is started after the start of supply of the reaction solution, and the supply of the reaction solution is ended after the supply of the liquid sample is ended. However, the reverse is also possible.

[0063] Hydride generation is a well-known analytical method that utilizes reactions in the spray chamber AA. For example, when analyzing a liquid sample containing arsenic or antimony, a sodium borohydride solution is used as the reaction liquid. In the spray chamber AA, arsenic or antimony is converted into a volatile hydride, AsH ３ or SbH ３ The vaporized solution is discharged from the sample outlet 55 and is subjected to analysis.

[0064] Known spray chambers used in hydride generation methods include the Multimode Sample Introduction System (MSIS) manufactured by Agilent Technologies and the HydraMist manufactured by Glass Expansion Corp. In both of these conventional spray chambers, the area over which the reaction liquid flows is small, resulting in slow reaction and vaporization rates.

[0065] In contrast, in the spray chamber AA of this embodiment, the reaction liquid spreads over a wide area as a liquid film flow inside, improving the reaction rate and vaporization rate of the sample, thereby increasing the analytical sensitivity of the analyzer.

[0066] The reaction occurring inside the spray chamber AA is not limited to the hydride generation reaction, but other reactions can also be utilized. For example, if an alkaline solution such as sodium hydroxide solution is used as the reaction liquid, a neutralization reaction occurs with the acid (hydrochloric acid, nitric acid, acetic acid, hydrofluoric acid, etc.) vaporized from the sample droplets. This allows for a reduction in the amount of acid introduced into the EI excitation / ionization source.

[0067] Using a non-volatile aqueous sulfuric acid solution as the reaction liquid can reduce alkaline vapors such as ammonia. In plasma mass spectrometry, interference from polyatomic ions caused by chlorine, carbon, nitrogen, sulfur, etc. can be a problem, but this method is effective in reducing this interference. Furthermore, because the sulfuric acid supplied as the reaction liquid is not atomized, it is not introduced into the EI excitation / ionization source. Therefore, there is no increase in interfering components such as polyatomic ions caused by sulfur.

[0068] The reaction liquid may contain a masking agent, a complexing agent, etc. If the liquid sample contains hydrofluoric acid, it reacts with silica to form SiF ４ It is known that mixing 6 mL of a 6% boric acid solution with 1 mL of 40% hydrofluoric acid can mask the hydrofluoric acid. If a boric acid solution is used as the reaction liquid, the wall surfaces 41i, 41o, and 42i of the spray chamber AA can be covered with a liquid film flow of the boric acid solution. Therefore, if the hydrofluoric acid concentration of the liquid sample is low, glass inner tube 41 and outer tube 42 can be used. In addition to boric acid, solutions containing calcium, aluminum, etc., which easily form complexes with fluoride ions, can also be used as the reaction liquid.

[0069] It is also known that the memory effect of mercury can be reduced by using a solution containing 0.001% L-cysteine ​​or 10 ng / mL gold (Au). The use of these as reaction solutions can reduce the memory effect of mercury.

[0070] As the reaction liquid, various solutions that cause neutralization reactions, oxidation-reduction reactions, derivatization reactions, etc., and slurries containing catalysts (for example, photocatalysts such as titanium dioxide) can also be used.

[0071] Almost the entire wall surfaces 41i, 41o, 42i of the inner pipe 41 and the outer pipe 42 can be covered with a liquid film flow of a liquid containing pure water, a neutralizing liquid, a masking agent, or the like. Therefore, metals such as stainless steel and titanium, and plastics such as acrylic resin and polycarbonate, which could not be used conventionally due to their acid and alkali resistance, can be used as materials for the inner pipe 41 and the outer pipe 42. This allows the spray chamber AA to be manufactured at low cost.

[0072] Depending on the type of reaction, a higher temperature may accelerate the reaction. In such cases, a heated reaction solution may be supplied to the spray chamber AA. The reaction solution may be heated to a temperature higher than room temperature (25°C). The temperature of the reaction solution is set to a temperature appropriate for the type of reaction.

[0073] (3) Combination The first, second, and third liquid supply sources 30A, 30B, and 30C can each supply liquids of different compositions or temperatures to the spray chamber AA. That is, liquid film flows of liquids of different compositions or temperatures can be formed on the inner pipe inner wall surface 41i, the inner pipe outer wall surface 41o, and the outer pipe inner wall surface 42i. Several examples utilizing this will be described below.

[0074] Example 1: A liquid film flow of a reaction liquid at room temperature (20-25°C) is formed on the inner wall surface 41i of the inner tube, a liquid film flow of pure water at room temperature is formed on the outer wall surface 41o of the inner tube, and a liquid film flow of cooled pure water (e.g., 2°C) is formed on the inner wall surface 42i of the outer tube. In this way, chemical reactions such as hydride generation reactions occur at a sufficient rate in the internal space of the inner tube 41. Furthermore, sample droplets are cooled in the space between the outer tube 42 and the inner tube 41, reducing the amount of water vapor introduced into the EI, such as the excitation / ionization source. If the liquid flowing on the inner wall surface 42i of the outer tube contains sodium hydroxide, acid vapors such as hydrochloric acid and nitric acid can also be removed.

[0075] Example 2: A liquid film flow of a heated reaction solution is formed on the inner wall surface 41i of the inner tube, a liquid film flow of pure water at room temperature is formed on the outer wall surface 41o of the inner tube, and a liquid film flow of cooled pure water (for example, 10°C) is formed on the inner wall surface 42i of the outer tube. Depending on the type of reaction, a relatively high temperature may be required. For example, osmium is oxidized to form osmium tetroxide (OsO ４ In the method of vaporizing the potassium dichromate solution as a solution containing potassium dichromate, a temperature of 70° C. or higher is preferred. In this case, a potassium dichromate solution heated to 70° C. or higher is supplied to the inner wall surface 41i of the inner tube. This makes it possible to achieve both a sufficient oxidation reaction rate and a reduction in the amount of water vapor.

[0076] Example 3: A liquid film flow of cooled cleaning liquid is formed on the inner wall surface 41i of the inner tube, and neither cleaning liquid nor reaction liquid is supplied to the outer wall surface 41o of the inner tube nor the inner wall surface 42i of the outer tube. The spray chamber AA is then heated from the outside using a heating means such as a heater or infrared rays. The sample droplets are cooled in the inner space of the inner tube 41, thereby reducing the amount of water vapor. Furthermore, the fine droplets are heated as they pass through the space between the outer tube 42 and the inner tube 41, further reducing their particle size. This improves the transport efficiency of the sample droplets to the excitation / ionization source, such as EI, as well as the excitation and ionization efficiencies.

[0077] The amount of water vapor introduced into the EI is the same because the water vapor evaporated from the droplets due to heating is also introduced into the EI. However, the microenvironment of the target element in the EI is different between water vapor and droplets. The smaller the sample droplets, the higher the excitation and ionization efficiencies.

[0078] Second Embodiment Next, a spray chamber BB according to a second embodiment will be described. As shown in Fig. 6, the spray chamber BB according to this embodiment has first, second, and third liquid introduction passages 60A, 60B, and 60C integrally formed with an inner tube 41 and an outer tube 42.

[0079] A first annular passage 63A is formed at the upper edge of the inner pipe 41. A first liquid supply port 61A is connected to the first annular passage 63A. A cylindrical first auxiliary wall 65A is inserted into the upper part of the inner pipe 41. A first liquid film forming passage 64A is formed between the first auxiliary wall 65A and the inner pipe inner wall surface 41i. An opening at the lower edge of the first liquid film forming passage 64A is a first liquid delivery port 62A. The end cap 51 is inserted into the first auxiliary wall 65A. The cleaning liquid supplied to the first liquid supply port 61A passes through the first annular passage 63A, flows into the first liquid film forming passage 64A, and is delivered in the form of a film from the first liquid delivery port 62A to the inner pipe inner wall surface 41i.

[0080] A second annular passage 63B is formed on the outer periphery of the upper part of the inner pipe 41. A second liquid supply port 61B is connected to the second annular passage 63B. A cylindrical second auxiliary wall 65B surrounding the inner pipe 41 is provided below the second annular passage 63B. A second liquid film forming passage 64B is formed between the second auxiliary wall 65B and the inner pipe outer wall surface 41o. An opening at the lower edge of the second liquid film forming passage 64B is a second liquid delivery port 62B. The cleaning liquid supplied to the second liquid supply port 61B passes through the second annular passage 63B, flows into the second liquid film forming passage 64B, and is delivered in the form of a film from the second liquid delivery port 62B to the inner pipe outer wall surface 41o.

[0081] A third annular passage 63C is formed at the upper edge of the outer pipe 42. A third liquid supply port 61C is connected to the third annular passage 63C. A cylindrical third auxiliary wall 65C is inserted into the upper part of the outer pipe 42. A third liquid film forming passage 64C is formed between the third auxiliary wall 65C and the outer pipe inner wall surface 42i. An opening at the lower edge of the third liquid film forming passage 64C is a third liquid delivery port 62C. The lower edge of the second auxiliary wall 65B and the upper edge of the third auxiliary wall 65C are connected. The cleaning liquid supplied to the third liquid supply port 61C passes through the third annular passage 63C, flows into the third liquid film forming passage 64C, and is delivered in the form of a film from the third liquid delivery port 62C to the outer pipe inner wall surface 42i.

[0082] The sample outlet 55 is provided at the top of the third auxiliary wall 65C. A liquid film flow guide 71 is provided on the third auxiliary wall 65C so as to surround the connection with the sample outlet 55. The liquid film flow guide 71 may have any shape that prevents the inflow of liquid, and may be a protrusion as shown in Figure 6 or a groove.

[0083] Even if the cleaning liquid discharged from the second liquid discharge outlet 62B or the third liquid discharge outlet 62C flows onto the inner surface of the third auxiliary wall 65C for some reason, the liquid film flow guide 71 can prevent the cleaning liquid from flowing into the sample discharge outlet 55.

[0084] As shown in Figure 7, the first auxiliary wall 65A has a wedge-shaped cross section at its discharge-side edge (lower edge) on the liquid-contacting side (the side facing the first liquid film forming path 64A) with an acute angle. The second auxiliary wall 65B also has a wedge-shaped cross section at its discharge-side edge (lower edge) on the liquid-contacting side (the side facing the second liquid film forming path 64B). By making the discharge-side edges of the auxiliary walls 65A and 65B wedge-shaped in this way, liquid is less likely to adhere to the edges, preventing the liquid from dripping and falling. This allows for smooth liquid film flows to be delivered from the first and second liquid delivery ports 62A and 62B.

[0085] Third Embodiment Next, a spray chamber CC of a third embodiment will be described. As shown in Figures 8 and 9, the spray chamber CC of this embodiment is a so-called cyclone-type spray chamber. The spray chamber CC has a cyclone tube 43. The cyclone tube 43 is a circular tube with an expanded middle and conical upper and lower portions. A drain outlet 53 is provided at the lower end of the cyclone tube 43. A sample outlet 55 is provided at the upper end of the cyclone tube 43. An end cap holder tube 44 is connected to the middle of the cyclone tube 43 at an eccentric position.

[0086] An end cap 51 is inserted into the end cap holding tube 44. The end cap 51 holds the nebulizer 10. The nebulizer 10 atomizes the liquid sample and sprays the sample droplets into the inside of the end cap holding tube 44. The sprayed sample droplets swirl clockwise in FIG. 9 along the inner wall surface 43i of the cyclone tube 43. Droplets with relatively large diameters among the sample droplets collide with and adhere to the inner wall surface 43i, becoming drain and being discharged from the drain outlet 53. Only droplets with relatively small diameters among the sample droplets are discharged from the sample outlet 55.

[0087] In this way, the cyclone tube 43 and the end cap holding tube 44 form a flow path for the sample droplets. The cyclone tube 43 and the end cap holding tube 44 each correspond to the "flow path tube" described in the claims.

[0088] A liquid introduction passage 60 is formed integrally with the cyclone tube 43. An annular passage 63 is formed on the upper outer periphery of the cyclone tube 43. A liquid supply port 61 is connected to the annular passage 63. A cylindrical auxiliary wall 65 is inserted into the upper part of the cyclone tube 43. A liquid film formation passage 64 is formed between the auxiliary wall 65 and the inner wall surface 43i of the cyclone tube 43. An opening at the lower edge of the liquid film formation passage 64 is the liquid delivery outlet 62. The sample discharge port 55 is provided at the upper end of the auxiliary wall 65.

[0089] When cleaning liquid is supplied to the liquid supply port 61, the cleaning liquid passes through the annular path 63, flows into the liquid film forming path 64, and is delivered to the inner wall surface 43i from the liquid delivery port 62 in the form of a film. This forms a liquid film flow that covers almost the entire inner wall surface 43i. The cleaning liquid that flows down along the inner wall surface 43i is discharged from the drain discharge port 53.

[0090] The liquid supply port 61 may be connected in a normal direction or a tangential direction to the annular passage 63. If the liquid supply port 61 is connected in a tangential direction to the annular passage 63, the cleaning liquid flows circumferentially along the annular passage 63 and is delivered to the inner wall surface 43i while swirling. The centrifugal force of the swirling makes it easy for the cleaning liquid to flow along the inner wall surface 43i, so that the cleaning liquid can be prevented from dropping as droplets even in the conical portion at the top of the cyclone tube 43.

[0091] A liquid film flow guide 71 is provided on the inner wall surface 43i of the cyclone tube 43 so as to surround the connecting portion with the end cap holding tube 44. The cleaning liquid flowing down the inner wall surface 43i is obstructed by the liquid film flow guide 71, and is prevented from flowing into the end cap holding tube 44. This makes it possible to prevent the cleaning liquid from flowing into the end cap 51 and the nebulizer 10.

[0092] [Fourth Embodiment] Next, a spray chamber DD of the fourth embodiment will be described. As shown in Figure 10, the spray chamber DD of this embodiment is a cyclone-type spray chamber having a sample discharge pipe 45. The sample discharge pipe 45 is a relatively thin circular pipe and is arranged along the central axis of the cyclone pipe 43. The lower end of the sample discharge pipe 45 is open, and the internal space of the cyclone pipe 43 and the internal space of the sample discharge pipe 45 are in communication. A sample discharge port 55 is provided at the upper end of the sample discharge pipe 45.

[0093] The sample droplets sprayed from the nebulizer 10 swirl along the inner wall surface 43i of the cyclone tube 43. Among the sample droplets, droplets with a relatively large diameter collide with and adhere to the inner wall surface 43i of the cyclone tube 43 and the outer wall surface 45o of the sample discharge tube 45, and become drain and are discharged from the drain discharge port 53. Among the sample droplets, only droplets with a relatively small diameter rise inside the sample discharge tube 45 and are discharged from the sample discharge port 55.

[0094] Therefore, in this embodiment, a flow path for sample droplets is formed by the cyclone tube 43, the end cap holding tube 44, and the sample discharge tube 45. The cyclone tube 43, the end cap holding tube 44, and the sample discharge tube 45 each correspond to a "flow path tube" in the claims.

[0095] First and second liquid introduction paths 60A, 60B are integrally formed with the cyclone tube 43. A first annular path 63A is formed around the sample discharge tube 45 at the upper edge of the cyclone tube 43. A first liquid supply port 61A is connected to the first annular path 63A. A first liquid film formation path 64A is formed between the inner wall surface 43i at the top of the cyclone tube 43 and the outer wall surface 45o of the sample discharge tube 45. An opening at the lower edge of the first liquid film formation path 64A is a first liquid delivery port 62A.

[0096] When cleaning liquid is supplied to the first liquid supply port 61A, the cleaning liquid passes through the first annular path 63A, flows into the first liquid film forming path 64A, and is then discharged from the first liquid delivery port 62A in the form of a film onto the inner wall surface 43i of the cyclone tube 43 and the outer wall surface 45o of the sample discharge tube 45. This forms a liquid film flow that covers almost the entire inner wall surface 43i and the outer wall surface 45o. The cleaning liquid that flows down along the inner wall surface 43i and the outer wall surface 45o is discharged from the drain discharge port 53.

[0097] A second annular passage 63B is formed on the outer periphery of the upper part of the sample discharge pipe 45. A second liquid supply port 61B is connected to the second annular passage 63B. A cylindrical second auxiliary wall 65B surrounding the sample discharge pipe 45 is provided above the second annular passage 63B. A second liquid film forming passage 64B is formed between the second auxiliary wall 65B and the outer wall surface 45o of the sample discharge pipe 45. An opening at the upper edge of the second liquid film forming passage 64B is a second liquid delivery port 62B. The sample discharge port 55 is provided at the upper end of the second auxiliary wall 65B.

[0098] When the cleaning liquid is supplied to the second liquid supply port 61B, the cleaning liquid passes through the second annular path 63B, rises in the second liquid film forming path 64B, and passes through the second liquid delivery port 62B over the upper edge of the sample discharge pipe 45, and is delivered in the form of a film onto the inner wall surface 45i of the sample discharge pipe 45. This forms a liquid film flow that covers almost the entire inner wall surface 45i. The cleaning liquid that flows down along the inner wall surface 45i is discharged from the drain discharge port 53.

[0099] A groove-shaped liquid film flow guide 72 is provided on the inner wall surface 43i of the cyclone tube 43 so as to surround the connecting portion with the end cap holding tube 44. The cleaning liquid flowing down the inner wall surface 43i is obstructed by the liquid film flow guide 72, and is prevented from flowing into the end cap holding tube 44. This makes it possible to prevent the cleaning liquid from flowing into the end cap 51 and the nebulizer 10.

[0100] Fifth Embodiment Next, a spray chamber EE according to a fifth embodiment will be described. As shown in FIG. 11 , first, second, and third liquid introduction passages 60A, 60B, and 60C are integrally formed with the cyclone tube 43. A first annular passage 63A is formed around the upper outer periphery of the cyclone tube 43. A first liquid supply port 61A is connected to the first annular passage 63A. A cylindrical first auxiliary wall 65A is inserted into the upper portion of the cyclone tube 43. A first liquid film formation passage 64A is formed between the first auxiliary wall 65A and the inner wall surface 43i of the cyclone tube 43. An opening at the lower edge of the first liquid film formation passage 64A is a first liquid delivery port 62A. The cleaning liquid supplied to the first liquid supply port 61A passes through the first annular passage 63A, flows into the first liquid film formation passage 64A, and is delivered from the first liquid delivery port 62A to the inner wall surface 43i in the form of a film.

[0101] A second annular passage 63B is formed above the first annular passage 63A around the sample discharge pipe 45. A second liquid supply port 61B is connected to the second annular passage 63B. A cylindrical second auxiliary wall 65B is provided below the second annular passage 63B, surrounding the sample discharge pipe 45. A second liquid film forming passage 64B is formed between the second auxiliary wall 65B and the outer wall surface 45o of the sample discharge pipe 45. An opening at the lower edge of the second liquid film forming passage 64B is a second liquid delivery port 62B. The upper edge of the first auxiliary wall 65A and the lower edge of the second auxiliary wall 65B are connected. The cleaning liquid supplied to the second liquid supply port 61B passes through the second annular passage 63B, flows into the second liquid film forming passage 64B, and is delivered from the second liquid delivery port 62B in the form of a film onto the outer wall surface 45o.

[0102] A third annular passage 63C is formed on the upper outer periphery of the sample discharge pipe 45. A third liquid supply port 61C is connected to the third annular passage 63C. A cylindrical third auxiliary wall 65C is provided above the third annular passage 63C, surrounding the sample discharge pipe 45. A third liquid film forming passage 64C is formed between the third auxiliary wall 65C and the outer wall surface 45o of the sample discharge pipe 45. An opening at the upper edge of the third liquid film forming passage 64C is a third liquid delivery port 62C. When cleaning liquid is supplied to the third liquid supply port 61C, the cleaning liquid passes through the third annular passage 63C, rises within the third liquid film forming passage 64C, and flows from the third liquid delivery port 62C over the upper edge of the sample discharge pipe 45, and is delivered in the form of a film to the inner wall surface 45i of the sample discharge pipe 45.

[0103] [Sixth Embodiment] Next, a spray chamber FF of a sixth embodiment will be described. As shown in Figures 12 and 13, the spray chamber FF of this embodiment has a cyclone pipe 43. A liquid introduction passage 60 is integrally formed with the cyclone pipe 43. An annular passage 63 is formed at the connection between the middle and lower parts of the cyclone pipe 43. A liquid supply port 61 is connected to the annular passage 63. A cylindrical auxiliary wall 65 is provided inside the middle part of the cyclone pipe 43. A liquid film formation passage 64 is formed between the auxiliary wall 65 and the cyclone pipe 43. The opening at the upper edge of the liquid film formation passage 64 is a liquid delivery outlet 62.

[0104] Since the end cap holding pipe 44 is connected to the middle part of the cyclone pipe 43, the annular passage 63, the liquid film forming passage 64, and the liquid delivery outlet 62 are not formed in that part. In this way, the annular passage 63, the liquid film forming passage 64, and the liquid delivery outlet 62 are not limited to being completely connected annular, but may be partially disconnected annular.

[0105] When cleaning liquid is supplied to the liquid supply port 61, the cleaning liquid passes through the annular path 63, rises in the liquid film forming path 64, passes through the liquid delivery port 62, passes over the upper edge of the auxiliary wall 65, and is delivered in the form of a film onto the inner wall surface 43i of the cyclone pipe 43. As a result, a liquid film flow is formed on the middle or lower part of the inner wall surface 43i of the cyclone pipe 43. The cleaning liquid that flows down along the inner wall surface 43i is discharged from the drain discharge port 53.

[0106] 14 and 15, the spray chamber GG of this embodiment has a cyclone tube 43 and an end cap holding tube 44.

[0107] A first liquid introduction passage 60A is integrally formed with the cyclone pipe 43. A first annular passage 63A is formed on the upper outer periphery of the cyclone pipe 43. A first liquid supply port 61A is connected to the first annular passage 63A. A cylindrical first auxiliary wall 65A is inserted into the upper part of the cyclone pipe 43. A first liquid film formation passage 64A is formed between the first auxiliary wall 65A and the inner wall surface 43i of the cyclone pipe 43. An opening at the lower edge of the first liquid film formation passage 64A is a first liquid delivery outlet 62A. The cleaning liquid supplied to the first liquid supply port 61A passes through the first annular passage 63A, flows into the first liquid film formation passage 64A, and is delivered from the first liquid delivery outlet 62A in the form of a film onto the inner wall surface 43i.

[0108] The spray chamber GG has a second liquid introduction passage 60B on the end cap 51 side. A circumferential groove is formed on the outer peripheral surface of the end cap 51. When the end cap 51 is inserted into the end cap holding tube 44, a second annular passage 63B is formed along the circumferential direction of the end cap holding tube 44. The end cap holding tube 44 is provided with a second liquid supply port 61B that communicates with the second annular passage 63B. A second liquid film formation passage 64B is also formed between the outer peripheral surface of the tip of the end cap 51 and the inner wall surface 44i of the end cap holding tube 44. The opening of the second liquid film formation passage 64B is the second liquid delivery port 62B. The cleaning liquid supplied to the second liquid supply port 61B passes through the second annular passage 63B, flows into the second liquid film formation passage 64B, and is delivered to the inner wall surface 44i from the second liquid delivery port 62B in the form of a film.

[0109] In addition, a gap is formed between the outer peripheral surface of nebulizer 10 and the inner peripheral surface of end cap 51. End cap holding tube 44 is provided with sheath gas supply port 52 that communicates with the gap. When sheath gas is supplied from sheath gas supply port 52, the sheath gas is sprayed from the outer periphery of nebulizer 10. The sheath gas can prevent sample droplets from adhering to the tip of nebulizer 10.

[0110] Sample droplets tend to adhere to the connection between the cyclone tube 43 and the end cap holding tube 44, and to the area around the tip of the nebulizer 10, and cleaning is difficult in spray chambers with conventional configurations. In contrast, the spray chamber GG of this embodiment sprays cleaning liquid from the outer periphery of the end cap 51, so that adhering sample droplets can be efficiently cleaned.

[0111] Because the second liquid outlet 62B opens horizontally, the range in which the liquid film flow is formed varies depending on the speed at which the cleaning liquid is discharged. The faster the discharge speed, the wider the range in which the liquid film flow can be formed. As shown in Figure 16(A), if the opening width of the second liquid outlet 62B (the distance between the end cap 51 and the end cap holding tube 44) is made uniform around the entire circumference, the cleaning liquid is discharged at approximately the same speed around the entire circumference of the end cap holding tube 44.

[0112] As shown in Figure 16(B), a portion of the circumferential area of ​​the second liquid film forming path 64B and the second liquid outlet 62B may be blocked. In this case, a liquid film flow is discharged only from the open portion of the second liquid outlet 62B, allowing a liquid film flow to be formed in a concentrated manner in a specific area. Sample droplets tend to adhere to the portion of the inner wall surface 43i of the cyclone tube 43 that faces the nebulizer 10. For example, a liquid film flow of the cleaning liquid may be formed in a concentrated manner in such an area where sample droplets tend to adhere.

[0113] Alternatively, the reaction liquid may be delivered from the partially blocked second liquid delivery port 62B, forming a liquid film flow of the reaction liquid concentrated in an area where the sample droplets are likely to adhere. This allows the sample droplets and the reaction liquid to come into contact efficiently, thereby increasing the reaction efficiency even with a small amount of reaction liquid.

[0114] As shown in Figure 16(C), the second liquid discharge outlet 62B may be configured with multiple small openings arranged in a ring. For example, if the second liquid film formation path 64B is configured with multiple narrow paths connecting the second annular path 63B and the liquid discharge side, the second liquid discharge outlet 62B can be configured in this manner. Since the cleaning liquid can be discharged from the second liquid discharge outlet 62B at high speed, the area covered by the liquid film flow is wide. By adjusting the opening width and density of the multiple small openings, the discharge speed of the cleaning liquid can be changed, and the flow area of ​​the cleaning liquid can be adjusted.

[0115] Eighth Embodiment Next, a spray chamber HH according to an eighth embodiment will be described. The spray chamber HH according to this embodiment is constructed by attaching a spray chamber auxiliary tool 80 (hereinafter referred to as the auxiliary tool 80) to a commercially available spray chamber 100 having a conventional configuration.

[0116] Figure 17 shows a spray chamber 100 with a conventional configuration. The spray chamber 100 is a so-called Scott-type spray chamber. The spray chamber 100 has an inner tube 41 and an outer tube 42 that form a double tube. A drain outlet 53 is provided at the bottom of the outer tube 42, and a sample outlet 55 is provided at the top. The upper ends of the inner tube 41 and outer tube 42 are closed with end caps 151.

[0117] As shown in Figure 18, the spray chamber HH of this embodiment is configured by replacing the end cap 151 of the conventional spray chamber 100 with an auxiliary device 80. The auxiliary device 80 comprises an end cap 51 and a holder 54, and is attached to the upper ends of the inner tube 41 and the outer tube 42. The end cap 51 holds the nebulizer 10.

[0118] The auxiliary tool 80 has a liquid introduction path 60. A liquid supply port 61 is formed in the holder 54. An annular path 63 is formed at the joint between the end cap 51 and the holder 54. When the auxiliary tool 80 is attached to the inner pipe 41, the annular path 63 is an annular flow path that runs along the circumferential direction of the inner pipe 41. The liquid supply port 61 is in communication with the annular path 63.

[0119] The lower part of the end cap 51 forms a cylindrical auxiliary wall 65. The auxiliary wall 65 is inserted into the upper part of the inner pipe 41. When the auxiliary tool 80 is attached to the inner pipe 41, the auxiliary wall 65 is positioned with a gap between it and the inner pipe inner wall surface 41i, forming a liquid film formation path 64 between it and the inner pipe inner wall surface 41i. The opening at the lower edge of the liquid film formation path 64 is the liquid delivery outlet 62. Therefore, the liquid delivery outlet 62 is in contact with the inner pipe inner wall surface 41i and is an annular opening that follows the circumferential direction of the inner pipe 41.

[0120] The liquid supplied to the liquid supply port 61 flows circumferentially along the annular path 63, then flows into the liquid film forming path 64, and is delivered in the form of a film onto the inner pipe inner wall surface 41i from the liquid delivery port 62. The liquid forms a liquid film flow that covers almost the entire inner pipe inner wall surface 41i. The liquid that flows down along the inner pipe inner wall surface 41i is discharged from the drain discharge port 53.

[0121] In the spray chamber HH of this embodiment, if a cleaning liquid is supplied to the liquid supply port 61, large droplets are captured by the liquid film flow of the cleaning liquid, making it difficult for the sample to remain on the inner pipe inner wall surface 41i. It is also possible to form a liquid film flow of the reaction liquid on the inner pipe inner wall surface 41i. Moreover, by attaching the auxiliary tool 80 to an existing spray chamber 100, a configuration can be created in which a liquid film flow can be formed on the inner pipe inner wall surface 41i. This reduces equipment costs.

[0122] The auxiliary device 80 may be configured to form a liquid film flow on the outer wall surface of the inner pipe 41 and the inner wall surface of the outer pipe 42. As in the second embodiment, the outlet-side edge (lower edge) of the auxiliary wall 65 may be wedge-shaped. Furthermore, as in the seventh embodiment, a portion of the liquid delivery port 62 may be closed, or the liquid delivery port 62 may be configured to consist of a plurality of small openings.

[0123] Ninth Embodiment Next, a spray chamber JJ according to a ninth embodiment will be described. The spray chamber JJ according to this embodiment is configured by attaching a spray chamber auxiliary tool 90 (hereinafter referred to as the auxiliary tool 90) to a commercially available spray chamber 200 having a conventional configuration.

[0124] Figure 19 shows a spray chamber 200 of a conventional configuration. The spray chamber 200 is a so-called cyclone-type spray chamber. The spray chamber 200 has a cyclone pipe 43. A drain outlet 53 is provided at the lower end of the cyclone pipe 43. An end cap holding pipe 44 is connected to the middle of the cyclone pipe 43 at an eccentric position. An end cap 51 is inserted into the end cap holding pipe 44. The end cap 51 holds the nebulizer 10.

[0125] As shown in Figure 20, the spray chamber JJ of this embodiment has an auxiliary device 90 attached to the upper end of a cyclone tube 43. The auxiliary device 90 has an outer tube 92 with an O-ring 91 fitted on its inner surface. A liquid supply port 61 and an annular passage 63 are provided at the top of the outer tube 92. A cylindrical auxiliary wall 65 is provided inside the outer tube 92. A sample discharge port 55 is provided at the upper end of the auxiliary wall 65.

[0126] The auxiliary tool 90 is attached by inserting the upper end of the cyclone tube 43 into the outer cannula 92. An O-ring 91 forms a liquid seal between the inner surface of the outer cannula 92 and the outer surface of the cyclone tube 43. The lower part of the auxiliary wall 65 is inserted into the cyclone tube 43. A liquid film formation path 64 is formed between the auxiliary wall 65 and the inner wall surface 43i of the cyclone tube 43. The opening at the lower edge of the liquid film formation path 64 is the liquid delivery outlet 62.

[0127] The liquid supplied to the liquid supply port 61 passes through the annular path 63, flows into the liquid film forming path 64, and is delivered to the inner wall surface 43i from the liquid delivery port 62 in the form of a film. This forms a liquid film flow that covers almost the entire inner wall surface 43i. The liquid that flows down along the inner wall surface 43i is discharged from the drain discharge port 53.

[0128] In this way, by attaching the auxiliary tool 90 to the existing spray chamber 200, a configuration can be created in which a liquid film flow can be formed on the inner wall surface 43i of the cyclone pipe 43.

[0129] Tenth Embodiment Next, a spray chamber KK according to a tenth embodiment will be described. The spray chamber KK according to this embodiment has a liquid reservoir portion as a liquid dispersion portion of the liquid introduction passage.

[0130] 21, the spray chamber KK is a so-called Scott type spray chamber having an inner pipe 41 and an outer pipe 42. First, second and third liquid introduction passages 60A, 60B and 60C are formed in an end cap 51 and a flow passage forming body 56.

[0131] The first liquid introduction path 60A comprises a first liquid supply port 61A, a first communication path 66A, a first liquid storage section 67A, a first liquid film formation path 64A, and a first liquid delivery port 62A. The first liquid delivery port 62A is an annular opening that contacts the inner wall surface 41i of the inner pipe and follows the circumferential direction of the inner pipe 41. The liquid supplied to the first liquid supply port 61A flows through the first communication path 66A, the first liquid storage section 67A, and the first liquid film formation path 64A in this order, and is delivered from the first liquid delivery port 62A. The liquid delivered from the first liquid delivery port 62A forms a liquid film flow on the inner wall surface 41i of the inner pipe.

[0132] The second liquid introduction path 60B consists of a second liquid supply port 61B, a second communication passage 66B, a second liquid storage section 67B, a second liquid film forming path 64B, and a second liquid delivery port 62B (the second liquid supply port 61B and the second communication passage 66B are not shown in FIG. 21 ). The second liquid delivery port 62B is an annular opening that contacts the inner pipe outer wall surface 41o and follows the circumferential direction of the inner pipe 41. The liquid supplied to the second liquid supply port 61B flows through the second communication passage 66B, the second liquid storage section 67B, and the second liquid film forming path 64B in this order, and is delivered from the second liquid delivery port 62B. The liquid delivered from the second liquid delivery port 62B forms a liquid film flow on the inner pipe outer wall surface 41o.

[0133] The third liquid introduction path 60C comprises a third liquid supply port 61C, a third communication passage 66C, a third liquid storage section 67C, a third liquid film formation path 64C, and a third liquid delivery port 62C (the third liquid supply port 61C and the third communication passage 66C are not shown in FIG. 21 ). The third liquid delivery port 62C is an annular opening that contacts the outer tube inner wall surface 42i and follows the circumferential direction of the outer tube 42. The liquid supplied to the third liquid supply port 61C flows through the third communication passage 66C, the third liquid storage section 67C, and the third liquid film formation path 64C in this order, and is delivered from the third liquid delivery port 62C. The liquid delivered from the third liquid delivery port 62C forms a liquid film flow on the outer tube inner wall surface 42i.

[0134] 22, the flow path former 56 is composed of three members, namely, first, second, and third members 56A, 56B, and 56C. By vertically stacking these first, second, and third members 56A, 56B, and 56C and the end cap 51, first, second, and third liquid introduction paths 60A, 60B, and 60C are formed.

[0135] 23A, first, second, and third liquid supply ports 61A, 61B, and 61C are formed in the end cap 51. Furthermore, flow paths are formed inside the end cap 51, connecting the liquid supply ports 61A, 61B, and 61C to the bottom surface of the end cap 51. The flow paths connected to the first and second liquid supply ports 61A and 61B constitute part of first and second communication passages 66A and 66B, respectively. The flow path connected to the third liquid supply port 61C is a third communication passage 66C. The end cap 51 also has a sheath gas supply port 52.

[0136] 21 and 22, the third member 56C is a generally cylindrical member whose upper end is closed by a top plate. A side wall 67w is erected around the periphery of the top surface of the top plate of the third member 56C, and a disk-shaped recess is formed inside the side wall 67w. When the third member 56C is provided below the end cap 51, the space between the recess in the top surface of the top plate of the third member 56C and the bottom surface of the end cap 51 forms a third liquid storage portion 67C. A third communication passage 66C formed in the end cap 51 communicates with the third liquid storage portion 67C.

[0137] The insertion portion of nebulizer 10 and first and second communication passages 66A, 66B extend vertically through the top plate of third member 56C. Three tubes protrude from the top surface of third member 56C, separating third liquid storage section 67C from the insertion portion of nebulizer 10 and first and second communication passages 66A, 66B.

[0138] The third member 56C has a plurality of vertically extending grooves formed on its outer peripheral surface. As shown in Figure 23 (B) , when the third member 56C is inserted into the outer tube 42, the grooves on the outer peripheral surface of the third member 56C become the third liquid film forming path 64C. The lower ends of the grooves on the outer peripheral surface of the third member 56C become the third liquid delivery outlet 62C. The side wall 67w has cutouts in areas corresponding to the grooves. Therefore, the liquid in the third liquid storage section 67C flows down into the third liquid film forming path 64C.

[0139] As shown in Figures 21 and 22, the second member 56B is a generally disk-shaped member. A side wall 67w is erected around the periphery of the top surface of the top plate of the second member 56B, and a disk-shaped recess is formed inside the side wall 67w. When the second member 56B is inserted into the third member 56C, the space between the top surface of the second member 56B and the inner surface of the third member 56C forms a second liquid storage portion 67B. A second communication passage 66B formed in the end cap 51 and the third member 56C communicates with the second liquid storage portion 67B.

[0140] The insertion portion of nebulizer 10 and first communication passage 66A pass through second member 56B in the vertical direction. Two tubes protrude from the upper surface of second member 56B, separating second liquid storage section 67B from the insertion portion of nebulizer 10 and first communication passage 66A.

[0141] The second member 56B has a plurality of vertically extending grooves formed on its outer peripheral surface. As shown in FIG. 24A, when the second member 56B is inserted into the third member 56C, the grooves on the outer peripheral surface of the second member 56B become part of the second liquid film forming path 64B. The liquid in the second liquid storage portion 67B flows down into the second liquid film forming path 64B. As shown in FIG. 24B, the upper part of the inner tube 41 is also inserted into the third member 56C. The remainder of the second liquid film forming path 64B is formed between the inner peripheral surface of the third member 56C and the inner tube 41, and its lower end becomes the second liquid discharge outlet 62B.

[0142] 21 and 22, the first member 56A is a generally cylindrical member. A side wall 67w is erected around the periphery of the top surface of the first member 56A, and a disk-shaped recess is formed inside the side wall 67w. When the first member 56A is placed below the second member 56B, the space between the recess on the top surface of the first member 56A and the bottom surface of the second member 56B forms a first liquid storage portion 67A. The first communication passages 66A formed in the end cap 51 and the second and third members 56B and 56C communicate with the first liquid storage portion 67A.

[0143] The insertion portion of the nebulizer 10 passes through the first member 56A from top to bottom. A tube that separates the first liquid storage portion 67A and the insertion portion of the nebulizer 10 protrudes from the upper surface of the first member 56A.

[0144] A plurality of grooves are formed on the outer peripheral surface of the first member 56A, extending vertically. As shown in FIG. 24B, when the first member 56A is inserted into the inner tube 41, the grooves on the outer peripheral surface of the first member 56A become the first liquid film forming path 64A. The lower ends of the grooves on the outer peripheral surface of the first member 56A become the first liquid delivery outlet 62A. Notches are provided in the side wall 67w at portions corresponding to the grooves. Therefore, the liquid in the first liquid storage section 67A flows down into the first liquid film forming path 64A.

[0145] As described above, the first, second, and third liquid introduction paths 60A, 60B, and 60C have the first, second, and third liquid storage sections 67A, 67B, and 67C, respectively. The liquid supplied to each liquid supply port 61A, 61B, and 61C is temporarily stored in the liquid storage sections 67A, 67B, and 67C. This distributes the liquid, allowing it to be discharged evenly from the entire area of ​​the annular liquid delivery ports 62A, 62B, and 63C. In this way, the liquid storage sections 67A, 67B, and 67C function as liquid dispersion sections.

[0146] As shown in Figure 25(A), the liquid film forming path 64 may be configured to consist of multiple narrow paths arranged along the circumferential direction of the flow path pipe 40. The narrow paths may have the same width from the inlet side to the outlet side of the liquid. As shown in Figure 25(B), the narrow paths may have a shape in which the width increases from the inlet side to the outlet side of the liquid. This shape makes it easier to form a liquid film flow on the wall surface of the flow path pipe 40. As shown in Figure 25(C), the liquid film forming path 64 may be a completely cylindrical flow path. In this case, the liquid delivery outlet 62 becomes a continuous annular opening, making it easier to form a liquid film flow.

[0147] 26, the height of the liquid storage section 67 may be increased to increase the volume. In other words, the liquid storage section 67 may be shaped like a water tank. By shaping the liquid storage section 67 in this way, it is possible to prevent the formation of specific water paths within the liquid storage section 67. Therefore, the liquid can be guided evenly to the entire area of ​​the annular liquid delivery port 62.

[0148] As shown in Figure 27, the liquid storage section 67 may be filled with an impregnated body 68. The impregnated body 68 is a member into which the liquid permeates. The impregnated body 68 may be made of a porous material, a filter material obtained by bonding fibers, or the like. Since the liquid permeates the impregnated body 68, the liquid is more likely to spread throughout the liquid storage section 67. This allows the liquid to be more dispersed, allowing the liquid to be evenly guided to the entire area of ​​the liquid delivery port 62.

[0149] An impregnated body may be provided in the liquid film forming path 64. This also makes it possible to prevent the liquid from flowing unevenly in a certain region of the liquid delivery port 62.

[0150] As shown in FIG. 28(A), a liquid storage section 67 may be formed by providing a partition wall 68w on the outer surface of the impregnated body 68. The partition wall 68w may be formed by attaching a plate material to the outer surface of the impregnated body 68. Alternatively, the partition wall 68w may be formed by thermally fusing the surface of the porous or filter material that is the material for the impregnated body 68 or by impregnating it with an adhesive. The partition wall 68w may be provided in a portion of the impregnated body 68 where liquid does not flow. In the example shown in FIG. 28(A), partition walls 68w are provided on the upper and lower surfaces of the impregnated body 68 and at the insertion portion for the nebulizer 10. No partition wall 68w is provided on the outer periphery of the lower surface of the impregnated body 68. This portion is the liquid delivery outlet 62.

[0151] The partition wall 68w on the lower surface of the impregnated body 68 may be flat as shown in Fig. 28(A), may be dome-shaped as shown in Fig. 28(B), or may be cone-shaped as shown in Fig. 28(C). If the partition wall 68w on the lower surface of the impregnated body 68 is dome-shaped or cone-shaped, the liquid delivered from the liquid delivery port 62 is less likely to reach the partition wall 68w. Therefore, it is possible to prevent the liquid from dropping as droplets from the partition wall 68w on the lower surface of the impregnated body 68.

[0152] [Eleventh Embodiment] Next, a spray chamber LL of an eleventh embodiment will be described. As shown in Figure 29(A), the spray chamber LL of this embodiment has a cyclone pipe 43, and is a so-called cyclone type spray chamber.

[0153] The upper part of the cyclone tube 43 is cylindrical, and a flow path former 56 is inserted into the interior of the cylindrical part. A liquid introduction path 60 is formed in the flow path former 56. A sample discharge pipe 45 passes through the center of the flow path former 56.

[0154] The liquid introduction path 60 is made up of a liquid supply port 61, a liquid storage section 67, a liquid film forming path 64, and a liquid delivery port 62. The liquid delivery port 62 is an annular opening that contacts the inner wall surface 43i of the cyclone tube 43 and extends in the circumferential direction of the cyclone tube 43. The liquid supplied to the liquid supply port 61 flows through the liquid storage section 67 and the liquid film forming path 64 in this order, and is delivered from the liquid delivery port 62. The liquid delivered from the liquid delivery port 62 forms a liquid film flow on the inner wall surface 43i.

[0155] 29(B), the liquid storage section 67 is a disk-shaped space. The liquid film forming path 64 is made up of a plurality of narrow paths. The liquid delivery port 62 is made up of a plurality of small openings arranged in a ring shape.

[0156] As shown in Figures 30(A) and 30(B), the bottom surface of the flow path former 56 may be formed in an upwardly convex cone shape. In this case, the liquid introduction path 60 may have, in addition to a first liquid film formation path 64A and a first liquid delivery outlet 62A along the inner wall surface 43i of the cyclone tube 43, a second liquid film formation path 64B and a second liquid delivery outlet 62B along the outer wall surface of the sample discharge tube 45. The first liquid film formation path 64A and the second liquid film formation path 64B are connected to a common liquid reservoir 67. The liquid delivered from the first liquid delivery outlet 62A forms a liquid film flow on the inner wall surface 43i. The liquid delivered from the second liquid delivery outlet 62B forms a liquid film flow on the bottom surface of the flow path former 56.

[0157] In this case, the liquid introduction path 60 does not need to have the first liquid film formation path 64A and the first liquid delivery outlet 62A. The liquid delivered from the second liquid delivery outlet 62B forms a liquid film flow on the bottom surface of the flow path former 56 and the inner wall surface 43i of the cyclone tube 43.

[0158] 31(A) and 31(B), the lower end of the sample discharge pipe 45 may reach the bottom of the cyclone pipe 43. Alternatively, the bottom surface of the flow path forming body 56 may be a downwardly convex cone. The liquid discharged from the first liquid discharge port 62A forms a liquid film flow on the inner wall surface 43i, and also forms a liquid film flow on the bottom surface of the flow path forming body 56. The liquid discharged from the second liquid discharge port 62B forms a liquid film flow on the outer wall surface 45o of the sample discharge pipe 45.

[0159] In this case, the liquid introduction path 60 does not need to have the second liquid film forming path 64B and the second liquid delivery port 62B. The liquid delivered from the first liquid delivery port 62A forms a liquid film flow on the inner wall surface 43i, and also forms a liquid film flow on the bottom surface of the flow path formation body 56 and the outer wall surface 45o of the sample discharge tube 45.

[0160] [Twelfth Embodiment] Next, a spray chamber MM according to a twelfth embodiment will be described. The spray chamber MM according to this embodiment has a plurality of dispersion paths as a liquid dispersion section of the liquid introduction path.

[0161] As shown in Figure 32(A), the spray chamber MM is a so-called cyclone-type spray chamber having a cyclone tube 43. A flow path former 56 is inserted into the extension of the upper part of the cyclone tube 43. A sample discharge port 55 is provided in the conical part of the cyclone tube 43.

[0162] A liquid introduction path 60 is formed in the flow path forming body 56. The liquid introduction path 60 is composed of a liquid supply port 61, a dispersion path 69, a liquid film formation path 64, and a liquid delivery port 62. The liquid delivery port 62 is an annular opening that contacts the inner wall surface 43i of the cyclone tube 43 and extends in the circumferential direction of the cyclone tube 43. The liquid supplied to the liquid supply port 61 flows through the dispersion path 69 and the liquid film formation path 64 in this order, and is delivered from the liquid delivery port 62. The liquid delivered from the liquid delivery port 62 forms a liquid film flow on the inner wall surface 43i.

[0163] As shown in Figure 32 (B), a plurality of dispersion paths 69 are formed inside the flow path former 56, extending radially from the center toward the outer periphery. The center end of each dispersion path 69 is connected to the liquid supply port 61, and the outer periphery end is connected to the liquid film forming path 64. Therefore, the liquid supply port 61 is connected to multiple locations of the liquid delivery port 62 via the multiple dispersion paths 69. The liquid supplied to the liquid supply port 61 is dispersed by flowing through the multiple dispersion paths 69. This allows the liquid to be delivered evenly from the entire area of ​​the annular liquid delivery port 62. In this way, the multiple dispersion paths 69 function as a liquid dispersion section.

[0164] As shown in Figure 33, the sample discharge port 55 may be provided in an extension at the top of the cyclone tube 43. Alternatively, as shown in Figure 34, an extension may be provided at the bottom of the cyclone tube 43, with the drain discharge port 53 at the bottom of the extension tube and the sample discharge port 55 in the middle. In these cases, the liquid introduction path 60 shown in Figures 32(A) and 32(B) can also be used.

[0165] For example, if the insertion portion of the nebulizer 10 passes through the center of the flow path former 56, the plurality of branch paths 69 may be shaped to avoid the insertion portion of the nebulizer 10.

[0166] AT Sample atomization introduction device 10 Nebulizer 20 Sample supply source 30A, 30B, 30C Liquid supply source AA, BB, CC, DD, EE, FF, GG, HH, JJ, KK, LL, MM Spray chamber 40 Flow path tube 41 Inner tube 42 Outer tube 43 Cyclone tube 44 End cap holding tube 45 Sample discharge tube 51 End cap 52 Sheath gas supply port 53 Drain discharge port 54 Holder 55 Sample discharge port 56 Flow path forming body 60, 60A, 60B, 60C Liquid introduction path 61, 61A, 61B, 61C Liquid supply port 62, 62A, 62B, 62C Liquid delivery port 63, 63A, 63B, 63C Circular path 64, 64A, 64B, 64C: Liquid film forming path 65, 65A, 65B, 65C: Auxiliary wall 66A, 66B, 66C: Communication path 67, 67A, 67B, 67C: Liquid storage portion 68: Impregnated body 69: Dispersion path 71, 72: Liquid film flow guide 80, 90: Auxiliary device

Claims

1. A spray chamber comprising: an end cap for holding a nebulizer; a flow path pipe that forms part or all of a flow path for sample droplets supplied from the nebulizer; a sample outlet for discharging fine droplets of the sample droplets from the flow path; a drain outlet for discharging coarse droplets of the sample droplets from the flow path; and a liquid introduction path for introducing liquid into the flow path pipe, wherein the liquid introduction path has a liquid supply port and an annular liquid delivery port that contacts a wall surface of the flow path pipe and follows the circumferential direction of the flow path pipe, and the liquid supplied to the liquid supply port is delivered to the wall surface from the liquid delivery port.

2. The spray chamber according to claim 1, characterized in that the liquid discharged from the liquid discharge port forms a liquid film flow on the wall surface and is discharged from the drain discharge port.

3. A spray chamber according to claim 1 or 2, characterized in that the liquid introduction path has a liquid dispersion section that disperses the liquid supplied to the liquid supply port and guides it to the liquid delivery port.

4. A spray chamber according to claim 3, characterized in that the liquid dispersion section is an annular passage formed along the circumferential direction of the flow path pipe.

5. The spray chamber according to claim 3, characterized in that the liquid dispersion section is a liquid storage section that temporarily stores the liquid.

6. A spray chamber according to claim 5, characterized in that the liquid introduction passage has an impregnated body that is filled in the liquid storage section and into which the liquid permeates.

7. A spray chamber according to claim 3, characterized in that the liquid dispersion section comprises a plurality of dispersion paths connecting the liquid supply port and a plurality of portions of the liquid delivery port.

8. A spray chamber according to any one of claims 1 to 7, characterized in that the liquid delivery outlet is a completely connected annular opening.

9. A spray chamber according to any one of claims 1 to 7, characterized in that the liquid delivery outlet consists of a plurality of small openings arranged in a ring shape.

10. A spray chamber according to any one of claims 1 to 7, characterized in that a part of the circumferential area of ​​the liquid delivery outlet is closed.

11. A spray chamber as described in any one of claims 1 to 10, characterized in that the liquid introduction path has an auxiliary wall that is arranged across a gap from the wall surface and forms a liquid film formation path between the wall surface and the auxiliary wall, and the discharge side edge of the auxiliary wall has a wedge-shaped cross section with an acute angle on the liquid-contacting side.

12. A spray chamber according to any one of claims 1 to 11, characterized in that it has a liquid film flow guide that surrounds the sample outlet and inhibits the inflow of the liquid.

13. A spray chamber according to any one of claims 1 to 12, characterized in that it has a liquid film flow guide that surrounds the end cap and inhibits the inflow of the liquid.

14. An auxiliary device for a spray chamber, which is attached to a flow path pipe that forms part or all of the flow path of sample droplets supplied from a nebulizer, and which comprises a liquid introduction path for introducing liquid into the flow path pipe, the liquid introduction path having a liquid supply port and an annular liquid delivery port that contacts the wall surface of the flow path pipe and follows the circumferential direction of the flow path pipe when the auxiliary device is attached to the flow path pipe, and the liquid supplied to the liquid supply port is delivered to the wall surface from the liquid delivery port.

15. A sample atomization and introduction device comprising: a spray chamber to which the spray chamber according to any one of claims 1 to 13 or the spray chamber auxiliary device according to claim 14 is attached; and a nebulizer attached to the spray chamber.

16. A sample nebulization and introduction device as described in claim 15, characterized in that it comprises a sample supply source that supplies a liquid sample to the nebulizer, and a liquid supply source that supplies a cleaning liquid to the liquid supply port, wherein the liquid supply source supplies the cleaning liquid to the liquid supply port at least while the sample supply source is supplying the liquid sample to the nebulizer.

17. The sample atomization and introduction device according to claim 16, wherein the cleaning liquid is cooled.

18. A sample atomization and introduction device as described in claim 15, characterized in that it comprises a sample supply source that supplies a liquid sample to the nebulizer, and a liquid supply source that supplies a cleaning liquid to the liquid supply port, and after the supply of the liquid sample from the sample supply source to the nebulizer has been completed, the cleaning liquid is supplied from the liquid supply source to the liquid supply port.

19. A sample atomization and introduction device according to any one of claims 16 to 18, characterized in that the cleaning liquid contains a surfactant.

20. A sample atomization and introduction device as described in claim 15, characterized in that it comprises a sample supply source that supplies a liquid sample to the nebulizer, and a liquid supply source that supplies a reaction liquid to the liquid supply port, wherein the sample supply source supplies the liquid sample to the nebulizer while the liquid supply source simultaneously supplies the reaction liquid to the liquid supply port, causing the sample droplets and the reaction liquid to react within the spray chamber.

21. The sample atomization and introduction device according to claim 20, wherein the reaction liquid is heated.

22. A method for operating a sample atomization and introduction device according to claim 15, characterized in that a cleaning liquid is supplied to the liquid supply port at least while a liquid sample is being supplied to the nebulizer.

23. The method for operating a sample atomization and introduction device according to claim 22, wherein the cleaning liquid is cooled.

24. A method for operating a sample atomization and introduction device according to claim 15, characterized in that after the supply of the liquid sample to the nebulizer is completed, a cleaning liquid is supplied to the liquid supply port.

25. A method for operating a sample atomization and introduction device according to any one of claims 22 to 24, characterized in that the cleaning liquid contains a surfactant.

26. A method for operating a sample atomization and introduction device as described in claim 15, characterized in that a liquid sample is supplied to the nebulizer and a reaction liquid is supplied to the liquid supply port at the same time, and the sample droplets and the reaction liquid are reacted in the spray chamber.

27. The method for operating a sample atomization and introduction device according to claim 26, wherein the reaction liquid is heated.

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