WO2023145270A1 - Flow switching valve and manufacturing method therefor - Google Patents

Flow switching valve and manufacturing method therefor Download PDF

Info

Publication number
WO2023145270A1
WO2023145270A1 PCT/JP2022/045270 JP2022045270W WO2023145270A1 WO 2023145270 A1 WO2023145270 A1 WO 2023145270A1 JP 2022045270 W JP2022045270 W JP 2022045270W WO 2023145270 A1 WO2023145270 A1 WO 2023145270A1
Authority
WO
WIPO (PCT)
Prior art keywords
stator
flow path
switching valve
rotor seal
rotor
Prior art date
Application number
PCT/JP2022/045270
Other languages
French (fr)
Japanese (ja)
Inventor
綾乃 大坪
充彦 植田
裕至 原田
久雄 稲波
Original Assignee
株式会社日立ハイテク
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日立ハイテク filed Critical 株式会社日立ハイテク
Publication of WO2023145270A1 publication Critical patent/WO2023145270A1/en

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K11/00—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves
    • F16K11/02—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit
    • F16K11/06—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit comprising only sliding valves, i.e. sliding closure elements
    • F16K11/072—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit comprising only sliding valves, i.e. sliding closure elements with pivoted closure members
    • F16K11/074—Multiple-way valves, e.g. mixing valves; Pipe fittings incorporating such valves with all movable sealing faces moving as one unit comprising only sliding valves, i.e. sliding closure elements with pivoted closure members with flat sealing faces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K3/00—Gate valves or sliding valves, i.e. cut-off apparatus with closing members having a sliding movement along the seat for opening and closing
    • F16K3/02—Gate valves or sliding valves, i.e. cut-off apparatus with closing members having a sliding movement along the seat for opening and closing with flat sealing faces; Packings therefor
    • F16K3/04—Gate valves or sliding valves, i.e. cut-off apparatus with closing members having a sliding movement along the seat for opening and closing with flat sealing faces; Packings therefor with pivoted closure members
    • F16K3/06—Gate valves or sliding valves, i.e. cut-off apparatus with closing members having a sliding movement along the seat for opening and closing with flat sealing faces; Packings therefor with pivoted closure members in the form of closure plates arranged between supply and discharge passages
    • F16K3/08—Gate valves or sliding valves, i.e. cut-off apparatus with closing members having a sliding movement along the seat for opening and closing with flat sealing faces; Packings therefor with pivoted closure members in the form of closure plates arranged between supply and discharge passages with circular plates rotatable around their centres

Definitions

  • the present invention relates to a channel switching valve and a manufacturing method thereof.
  • a flow path switching valve is generally composed of a stator that connects pipes, a rotor seal, a rotor that rotates the rotor seal, and a housing that holds them.
  • the rotor is supported by a spring or the like, and the rotor seal is pressed against the stator by the rotor, thereby keeping the rotor seal flow path and the stator flow path liquid-tight. Rotation of the rotor enables flow path switching between the stator and the rotor.
  • Patent Document 1 discloses a flow path switching valve having a diamond-like carbon film (hereinafter referred to as "DLC film”) on the outermost surface of the stator and rotor seal.
  • DLC film diamond-like carbon film
  • the flow switching valve of US Pat. No. 6,200,000 has a protective coating between the stator and rotor, the protective coating being deposited on the adhesive interlayer and the adhesive interlayer by filtered cathodic vacuum arc (FCVA) deposition. DLC film. This DLC film can extend valve life under high pressure operating conditions.
  • FCVA filtered cathodic vacuum arc
  • the DLC film of the protective film of the flow path switching valve described in Patent Document 1 has an average roughness Ra of 0.025 ⁇ m or less on the contact surface with the stator, which is a mirror surface.
  • the stator and rotor seal may stick together due to intermolecular bonds called "ringing phenomenon". Sticking may occur.
  • the present invention has been made in view of such circumstances, and provides a long-life passage switching valve that avoids sticking between the stator and the rotor seal, and a method of manufacturing the same.
  • a flow path switching valve is configured to rotate a stator having a plurality of first through holes, a rotor seal rotating in contact with the stator and having a plurality of second through holes, and the rotor seal rotating. and a rotor.
  • a diamond-like carbon film is formed on the sliding surfaces of the rotor seal and the stator, and the DLC film has an average roughness Ra of 0.05 ⁇ m or more.
  • a method for manufacturing a flow path switching valve includes: a stator having a plurality of first through holes; a rotor seal rotating in contact with the stator and having a plurality of second through holes; in which the stator and the rotor seal as objects to be treated are placed on an arc ion plating device, and carbon and metal are separated by arc discharge is ionized to form a diamond-like carbon film (DLC film) on the surface of the object to be processed via an intermediate film.
  • the DLC film has an average roughness Ra of 0.05 ⁇ m or more.
  • FIG. 1 is a cross-sectional view of a channel switching valve 1 according to an embodiment
  • FIG. 4 is a top view of the rotor seal 12
  • FIG. 3 is a top view of a contact surface between a rotor seal 12 and a rotor 13
  • FIG. 3 is a cross-sectional view of a protective film 120 (a DLC film 121 and an intermediate film 122) formed on the stator 11 and the rotor seal 12
  • FIG. A method of forming the DLC film 121 of tetrahedral amorphous carbon by the arc ion plating method will be described.
  • FIG. 2 is a flow path schematic diagram of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1.
  • FIG. 2 is a flow path schematic diagram of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1.
  • FIG. FIG. 2 is an example of a graph of changes in rotational torque during pre-running of the flow path switching valve 1 of FIG. 1.
  • FIG. FIG. 5 is a schematic diagram for explaining extension of a scratch when a stator 11 and a rotor seal 12 reciprocate;
  • FIG. 5 is a schematic diagram for explaining extension of a scratch when a stator 11 and a rotor seal 12 reciprocate;
  • 3 shows the relationship between the film thickness and hardness of the DLC film 121 and the service life of the channel switching valve 1.
  • FIG. FIG. 7 shows a cross-sectional photograph of the end portion of the rotor seal channel of FIG. 4A. 4 shows changes in stator-side roughness Ra1 and seal-side roughness Ra2 before and after running-in, and the service life (usable number of times) of flow path switching valve 1 for samples 1 to 3 according to the present embodiment.
  • FIG. 1A is a cross-sectional view of the flow path switching valve 1 according to the embodiment (cross-sectional view taken along dashed line 19 in FIG. 1C), and FIG. 1B is a top view of the rotor seal 12.
  • FIG. 1C is a top view of the contact surface between the rotor seal 12 and the rotor 13.
  • FIG. 1D is a cross-sectional view of protective film 120 (DLC film 121 and intermediate film 122) formed on stator 11 and rotor seal 12. As shown in FIG.
  • the flow path switching valve 1 is composed of a stator 11, a rotor seal 12, a rotor 13, and a housing 15.
  • the stator 11 has a main body made of metal such as stainless steel (SUS316, hereinafter) or ceramic, and has a plurality of stator flow paths 111 to 116 formed so as to pass through the main body. (See FIG. 1C) The ends of the stator flow paths 111 to 116 are arranged on one circumference around the rotation axis of the rotor 13 in the stator 11 . Pipes (not shown) are connected to these stator flow paths 111-116.
  • the rotor seal 12 has a main body made of metal such as SUS316, ceramic, resin, or the like. ) rotor seal passages 131 , 132 , 133 . The surfaces of the stator 11 and the rotor seal 12 forming sliding surfaces are coated with a protective film 120 for improving wear resistance performance.
  • the protective film 120 is composed of a DLC film 121 and an intermediate film 122 to provide abrasion resistance (see FIG. 1D).
  • the rotor seal 12 is pressed against the stator 11 by a spring (not shown) of the rotor 13.
  • a spring not shown
  • a flow path formed by connecting the rotor seal flow path 132 and the stator flow paths 113 and 114 and a flow path formed by connecting the rotor seal flow path 133 and the stator flow paths 115 and 116 are formed. Further rotation of the rotor 13 may create another flow path (described in detail below).
  • a protective film 120 is provided in order to prevent liquid leakage between these channels and liquid leakage to the outside.
  • the rotor seal 12 is fixed to the rotor 13 by pins 16 and 17.
  • the rotor seal 12 rotates while sliding relative to the stator 11 by a motor (not shown) connected to the rotor 13 .
  • the rotation angle of the rotor 13 can be measured, for example, by equipping the motor with an encoder (not shown).
  • the protective film 120 formed on the sliding surfaces of the rotor seal 12 and the stator 11 will be described with reference to FIG. 1D.
  • DLC film diamond-like carbon film
  • a DLC film 121 is formed on the outermost surfaces of the stator 11 and the rotor seal 12, which are the contact surfaces of the stator 11 and the rotor seal 12, and the stator 11 and the rotor seal 12 are arranged so that the DLC films 121 slide against each other.
  • the DLC film 121 and intermediate film 122 can be formed by a technique called arc ion plating.
  • a DLC of tetrahedral amorphous carbon is formed on the DLC film 121 by an arc ion plating method.
  • Tetrahedral amorphous carbon is DLC that does not contain hydrogen ions.
  • FIG. 2 shows an example of a schematic configuration of an arc ion plating apparatus 300 capable of executing the arc ion plating method.
  • the arc ion plating apparatus 300 includes, as an example, a vacuum chamber 301, and the vacuum chamber 301 includes a rotary table 311 for holding an object 310 to be processed.
  • the vacuum chamber 301 further comprises a graphite cathode 302 from which the DLC film 121 is formed, and a metal target 303 used to form the intermediate film 122 .
  • the intermediate film 122 is mainly made of metal such as aluminum, chromium, titanium, and tungsten.
  • the material of the metal target 303 can be changed according to the material of the stator 11 and rotor seal 12.
  • the vacuum chamber 301 further includes a gas injection port 3012 for injecting argon gas 3011 and an evacuation port 3014 for evacuation 3013 .
  • a workpiece 310 (corresponding to the stator 11 and rotor seal 12 ) is placed on a rotary table 311 , and the rotary table 311 is connected to a bias power supply 312 .
  • a processing object 310 is electrically connected to a bias power supply 312 via a rotary table 311 . Thereby, the bias power supply 312 can apply a bias voltage to the processing object 310 .
  • a film forming process for the DLC film 121 and the intermediate film 122 will be described.
  • Argon gas 3011 is filled in the vacuum chamber 301 .
  • arc discharge is performed by an arc discharge generator (not shown) to ionize the carbon and metal of the cathode 302 of the graphite cathode and the metal target 303, and using the bias power supply 312, DLC and metal ions are processed. It pulls to the outermost surface of the object 310 . Thereby, the DLC film 121 and the intermediate film 122 are formed on the object 310 to be processed.
  • the DLC film 121 has an average vertical roughness Ra of 0.05 ⁇ m or more in the stage before the break-in operation described later. It is formed to 0.3 ⁇ m or less. Both the average roughness Ra1 of the DLC film 121 of the stator 11 (stator-side roughness Ra1) and the average roughness Ra2 of the DLC film 121 of the rotor seal 12 (seal-side roughness Ra2) are 0.05 ⁇ m or more and 0.3 ⁇ m or less. It is preferred to However, it is preferable that the value of the average roughness Ra2 be set to a value larger than the average roughness Ra1. By setting Ra2>Ra1, sticking between the stator 11 and the rotor seal 12 is more difficult to occur.
  • the DLC film 121 of the channel switching valve 1 has a hardness of 20 GPa to 60 GPa.
  • the hardness can be obtained by adjusting the bias voltage of bias power supply 312 during the process.
  • FIGS. 3A and 3B show schematic flow path diagrams of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1A.
  • 3A is a schematic diagram of the flow path obtained at a certain rotation angle
  • FIG. 3B is a schematic diagram of the flow path when the rotor 13 is rotated about 60 degrees from the state of FIG. 3A.
  • the liquid chromatograph 421 is composed of a liquid feed pump 422, a needle 423, a syringe pump 424, a channel switching valve 1, a separation column 426, a detector 427, a pipe P2, and a pipe P1 connecting them.
  • the stator channels 111, 112, 113, 114, 115, and 116 of the channel switching valve 1 are connected to the liquid feed pump 422, the separation column 426, the needle 423, the syringe pump 424, or the pipe P2.
  • the needle 423 is connected to the stator flow path 113
  • the syringe pump 424 is connected to the stator flow path 114
  • the stator flow path 113, rotor seal flow path 132, stator flow path 114, and syringe pump 424 are connected. is connected.
  • the flow path switching valve 1 is rotated 60 degrees in the sliding direction 211 of FIG. 3A to switch the flow path, and the state of FIG. 3B is obtained.
  • the sample SP is sucked by the syringe pump 424, and the needle 423, the stator flow channel 113, the rotor seal flow channel 131, the stator flow channel 112, the pipe P2, the stator flow channel 115, the rotor seal flow channel 132, A state of being sucked into the stator flow path 114 is obtained.
  • the eluent 429 sent by the liquid-sending pump 422 passes through the stator channel 111, the rotor seal channel 133, the stator channel 116, the separation column 426, the detector 427, and flows into the waste liquid tank 481. status is obtained.
  • the flow path switching valve 1 When the flow path switching valve 1 is rotated clockwise by 60 degrees in the sliding direction 212 from the state of FIG. 3B, the flow path switching valve 1 can return to the state of FIG. 3A.
  • the liquid-sending pump 422 In the state of FIG. 3A, the liquid-sending pump 422 is driven to send the eluent 429 to the stator channel 111, the rotor seal channel 131, and the stator channel 112, thereby removing the sample SP in the pipe P2. It can be sent to separation column 426 .
  • the sample SP is detected by the detector 427 after being separated by the separation column 426 .
  • the eluent After the detection operation is completed, the eluent is continued to be supplied for several seconds to wash the entire channel. Then return to the state of FIG. 3B for analysis of another sample. After that, by setting the states shown in FIGS. 3A and 3B and repeating the above operation, the inspection of the sample SP is continued.
  • the separation column 426 is filled with particles of several micrometers inside and has high fluid resistance. Further, in order to improve the sample separation performance of the separation column 426, the flow path diameter of the pipe P1 connected to the separation column 426 is designed to be approximately 0.1 mm, which similarly has large fluid resistance. Therefore, the liquid-sending pump 422 is configured to send the eluent 429 at a high pressure of several tens of MPa. On the other hand, since the syringe pump 424 is not connected to a pipe or the like having a large flow resistance, the liquid feeding pressure of the syringe pump 424 is set to a value close to the atmospheric pressure (0.1 MPa).
  • the liquid is delivered from the pump at a pressure of 30 to 120 MPa or more, and the valve must operate under this high pressure condition.
  • the valve In order to provide the contact surfaces of the stator 11 and the rotor seal 12 with sealing properties under high-pressure liquid feeding, it is necessary to press the stator 11 and the rotor seal 12 with a large force.
  • the flow path switching valve is configured so that the surface pressure of the contact surface between the stator 11 and the rotor seal 12 is about 60 to 150 MPa according to the hydraulic pressure used.
  • the roughness Ra of the outermost surface of each of the stator 11 and the rotor seal 12 is a value close to a mirror surface such as 0.025 ⁇ m or less, for example.
  • the stator 11 and the rotor seal 12 may stick due to intermolecular bonds called ringing phenomenon. In this case, the channel switching valve 1 may not operate.
  • the flow path switching valve 1 of the present embodiment includes a DLC film 121 as part of the protective film 120 on the outermost layers of the stator 11 and rotor seal 12 by arc ion plating.
  • the DLC film 121 has an outermost surface average roughness Ra of 0.05 ⁇ m or more, for example, 0.05 to 0.15 ⁇ m, before running-in, which will be described later. This effectively prevents the stator 11 and rotor seal 12 from sticking together. As a result, the contact surface between the stator 11 and the rotor seal 12 does not suffer from abnormal wear or seizure, and a long-life passage switching valve 1 can be provided.
  • the rotor 13 is repeatedly rotated in the counterclockwise sliding direction 211 and the clockwise sliding direction 212. Perform a running-in.
  • the break-in operation is to rotate (reciprocate) the rotor 13 about 100 to 3000 times in the sliding directions 211 and 212 while feeding the eluent 429 .
  • the outermost surface of the DLC film 121 is properly smoothed, and the average roughness Ra is reduced, and the stator 11 and the rotor seal 12 are not stuck to each other. That is, the stator 11 and the rotor seal 12 do not stick together at their contact surfaces, and a long-life valve can be provided.
  • cavitation cavitation phenomenon
  • the contact surface between the stator 11 and the rotor seal 12 wears, and the sealing performance between the two is reduced. is not maintained and the valve life may be shortened. Abraded portions of the contact surface due to this cavitation will be described with reference to FIG.
  • FIG. 5A and FIG. 5B schematically show an example of flaws at the ends of the flow path caused by cavitation.
  • the stator flow path 111 has a stator flow path end flaw 1111
  • the rotor seal flow path 131 has a rotor seal flow path end flaw 1311 .
  • stator channel end flaws 1111 extend in direction 1112 (FIG. 5A) and rotor seal channel end flaws 1311 extend in direction 1312 (FIG. 5B).
  • FIG. 5B the high-pressure rotor seal flow path 133, the stator flow path 111, the stator flow path flaw 1111, the low-pressure rotor seal flow path flaw 1311, and the rotor seal flow path 131 are formed. If it is connected, the sealing property cannot be maintained, and the risk of liquid leakage increases.
  • the extension degree of the flaw 1111 at the end of the stator flow path and the flaw 1311 at the end of the rotor seal flow path due to this cavitation varies depending on the thickness and hardness of the DLC film 121 formed on the stator 11 and the rotor seal 12. There was found. By considering the film thickness and hardness of the DLC film 121, it is possible to withstand wear due to cavitation, reduce the stretching speed of scratches, and extend the bulb life.
  • the graph in FIG. 6 shows the relationship between the film thickness and hardness of the DLC film 121 and the service life of the channel switching valve 1 .
  • the horizontal axis indicates the film thickness of the DLC film 121
  • the vertical axis indicates the hardness
  • the diameter of the circle in the graph indicates the service life of the flow path switching valve 1 when the DPC film 121 having a certain film thickness and hardness is adopted. show.
  • valve life is prolonged by adopting a DLC film with a hardness of 20 to 60 GPa, which is amorphous carbon formed by the arc ion plating method.
  • the life 501 is short when the DLC film 121 with a hardness of less than 20 GPa is used. This is presumably because the DLC film 121 has a low hardness, so that cavitation causes the scratches 1111 at the ends of the stator flow paths 111 to 116 and the scratches 1311 at the ends of the rotor seal flow path to extend at a high speed.
  • the bulb life 502 when the DLC film 121 with a hardness of 20 to 30 GPa is adopted is 1.5 times the bulb life 501 when the hardness is 20 GPa or less, and the DLC film 121 with a hardness of 30 to 40 GPa is adopted.
  • the valve life 503 when the hardness is 20 GPa or less is double the valve life 501 when the hardness is 20 GPa or less. It turned out to be 7 times the life 501.
  • the bulb life 505 when the DLC film 121 of 50 GPa to 60 GPa is adopted is double the bulb life 501 when the hardness is 20 GPa or less.
  • FIG. 7 shows an example of a cross-sectional photograph of the end portion of the rotor seal channel of FIG. 4A. This cross-sectional photograph is a photograph of a sample embedded in a resin to prepare a cross section and photographed with a microscope.
  • the sample shown in FIG. 7 includes a resin 603 for sample preparation, a DLC film 121, an intermediate film 122, and a base material 123 of SUS316 (stator 11 or rotor seal 12).
  • a resin 603 for sample preparation a DLC film 121, an intermediate film 122, and a base material 123 of SUS316 (stator 11 or rotor seal 12).
  • the film thickness of the DLC film 121 is larger than 1.5 ⁇ m, as shown in FIG.
  • it peels off from the base material 123 of SUS316 and is confirmed as a scratch.
  • a gap may be generated between the contact surfaces of the stator 11 and the rotor seal 12 and the liquid may leak from the flow path switching valve 1 .
  • the thickness of the DLC film 121 is less than 0.5 ⁇ m
  • the stator 11 and the rotor seal 12 are brought into contact with each other and a load is applied, cracks 602 are generated in the intermediate film 122, and the DLC film 121 and the intermediate film 122 become SUS316. It has been confirmed that the liquid may peel off from the base material 123 (stator and rotor seal) and leak from the flow path switching valve 1 .
  • the flow path switching valve 1 formed with the DLC film 121 having a film thickness of 0.5 ⁇ m to 1.5 ⁇ m as the protective film 120 is capable of preventing the stator 11 and the rotor seal 12 from adhering to each other and cavitation. It can be seen that the wear of the contact surface can be suppressed and the life of the flow path switching valve can be extended. From the above, it is preferable to employ the DLC film 121 having a film thickness of 0.5 ⁇ m to 1.5 ⁇ m and a hardness of 20 to 60 GPa.
  • FIG. 8 shows changes in the stator-side roughness Ra1 and the seal-side roughness Ra2 before and after the break-in, and the service life (usable number of times) of the flow path switching valve 1 for samples 1 to 3 according to the present embodiment. show.
  • FIG. 8 also shows changes in the maximum roughness Rz1 of the DLC film 121 on the stator 11 side and the maximum roughness Rz2 of the DLC film 121 on the rotor seal 12 side before and after the break-in.
  • the film thickness and hardness of the DLC film 121 in each sample are as shown in FIG.
  • both the stator-side roughness Ra1 and the seal-side roughness Ra2 are set within the range of 0.05 to 0.3 ⁇ m before running-in.
  • a lifetime greatly exceeding that of the conventional specular DLC film 121 was obtained.
  • the present invention is not limited to the above-described embodiments, and includes various modifications.
  • the above-described embodiments have been described in detail in order to explain the present invention in an easy-to-understand manner, and are not necessarily limited to those having all the described configurations.
  • it is possible to replace part of the configuration of one embodiment with the configuration of another embodiment and it is also possible to add the configuration of another embodiment to the configuration of one embodiment.
  • Reference Signs List 1 Flow path switching valve 11 Stator 12 Rotor seal 13 Rotor 15 Housing 111, 112, 113, 114, 115, 116 Stator flow path 120 Protective film 121 DLC film 122 Intermediate films 131, 132, 133 ... Rotor seal channel 300 ... Arc ion plating device 301 ... Vacuum chamber 302 ... Cathode 303 ... Metal target 310 ... Object to be processed 311 ... Rotary table 312 ... Bias power source 3011 ... Argon gas 3012 ... Gas injection port 3013 ... Evacuation 3014 ... Evacuation port 421 Liquid chromatograph 422 ... Liquid sending pump 423 ... Needle 424 ... Syringe pump 426 ... Separation column 427 ... Detector SP ... Sample 429 ... Eluent 481, 482 ... Waste liquid tanks P1, P2 ... Piping

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Multiple-Way Valves (AREA)

Abstract

The present invention provides a long-life flow switching valve that avoids sticking of a stator and a rotor seal. This flow switching valve (1) includes: a stator (11) that has a plurality of first through-holes; a rotor seal (12) that rotates while being in contact with the stator (11) and that has a plurality of second through-holes; and a rotor (13) that is configured to make the rotor seal (12) rotate. Diamond-like carbon films (DLC films) (121; surfaces of protective films 120) are formed on sliding surfaces of the rotor seal (12) and the stator (11), and the average roughness Ra of the DLC films (121) is 0.05 μm or larger.

Description

流路切替バルブ、及びその製造方法Flow path switching valve and manufacturing method thereof
　本発明は、流路切替バルブ、及びその製造方法に関する。 The present invention relates to a channel switching valve and a manufacturing method thereof.
　液体クロマトグラフなどの分析装置において、サンプル液や溶離液を順次分析装置に導入するために流路切替バルブが備えられている。流路切替バルブは、一般に、配管を接続するステータ、ロータシール、ロータシールを回転させるロータ、及び、それらを保持するハウジングから構成される。ロ－タはバネなどによって支持され、ロータシールはロータによりステ－タに押しつけられ、これによりロータシール流路、及びステータ流路の液密性が保たれている。ロータが回転することで、ステータとロータとの間で流路の切替が可能になる。 　Analytical instruments such as liquid chromatographs are equipped with channel switching valves to sequentially introduce sample liquids and eluents into the analytical instruments. A flow path switching valve is generally composed of a stator that connects pipes, a rotor seal, a rotor that rotates the rotor seal, and a housing that holds them. The rotor is supported by a spring or the like, and the rotor seal is pressed against the stator by the rotor, thereby keeping the rotor seal flow path and the stator flow path liquid-tight. Rotation of the rotor enables flow path switching between the stator and the rotor.
　流路切替バルブのロータシールは、ロータによりステ－タに押しつけられながら回転し摺動するため、ステータとの接触面が摩耗して、その結果、流路切替バルブの寿命が短くなるという問題がある。この接触面の摩耗を抑制するため、ステータやロータシールの最表面にダイヤモンドライクカーボン膜（以下、「ＤＬＣ膜」という）を備えた流路切替バルブが特許文献１に示されている。 Since the rotor seal of the flow path switching valve rotates and slides while being pressed against the stator by the rotor, the contact surface with the stator wears, resulting in the problem of shortening the life of the flow path switching valve. be. In order to suppress wear of the contact surface, Patent Document 1 discloses a flow path switching valve having a diamond-like carbon film (hereinafter referred to as "DLC film") on the outermost surface of the stator and rotor seal.
　特許文献１の流路切替バルブは、ステータ及びロータの間に保護被膜を有し、その保護被膜は、接着中間膜と、フィルタ処理陰極真空アーク（ＦＣＶＡ）蒸着によって接着中間膜上に蒸着されたＤＬＣ膜とを含む。このＤＬＣ膜により、高圧運転条件下でのバルブ寿命を延ばすことができる。 The flow switching valve of US Pat. No. 6,200,000 has a protective coating between the stator and rotor, the protective coating being deposited on the adhesive interlayer and the adhesive interlayer by filtered cathodic vacuum arc (FCVA) deposition. DLC film. This DLC film can extend valve life under high pressure operating conditions.
　しかし、特許文献１に記載された流路切替バルブの保護被膜のＤＬＣ膜は、ステータとの接触面の平均粗さＲａが０．０２５μｍ以下と鏡面状である。この場合、ステータとロータシールが「リンギング現象」とよばれる分子間結合による固着することがある。固着が発生する虞がある。 However, the DLC film of the protective film of the flow path switching valve described in Patent Document 1 has an average roughness Ra of 0.025 μm or less on the contact surface with the stator, which is a mirror surface. In this case, the stator and rotor seal may stick together due to intermolecular bonds called "ringing phenomenon". Sticking may occur.
特表２０１４－５２０２５０号公報Japanese Patent Publication No. 2014-520250
　本発明は、このような事情に鑑みてなされたものであり、ステータとロータシールの固着を回避し、長寿命な流路切替バルブ、及びその製造方法を提供するものである。 The present invention has been made in view of such circumstances, and provides a long-life passage switching valve that avoids sticking between the stator and the rotor seal, and a method of manufacturing the same.
　本発明の流路切替バルブは、複数の第１の貫通孔を有するステータと、前記ステータと接触しながら回転し複数の第２の貫通孔を有するロータシールと、前記ロータシールを回転させるよう構成されるロータとを備える。前記ロータシール及び前記ステータの摺動面にダイヤモンドライクカーボン膜（ＤＬＣ膜）が成膜されており、前記ＤＬＣ膜の平均粗さＲａは０．０５μｍ以上である。 A flow path switching valve according to the present invention is configured to rotate a stator having a plurality of first through holes, a rotor seal rotating in contact with the stator and having a plurality of second through holes, and the rotor seal rotating. and a rotor. A diamond-like carbon film (DLC film) is formed on the sliding surfaces of the rotor seal and the stator, and the DLC film has an average roughness Ra of 0.05 μm or more.
　また、本発明の流路切替バルブの製造方法は、複数の第１の貫通孔を有するステータと、前記ステータと接触しながら回転し複数の第２の貫通孔を有するロータシールと、前記ロータシールを回転させるよう構成されるロータとを備えた流路切替バルブの製造方法において、アークイオンプレーティング装置に、処理対象物としての前記ステータ及び前記ロータシールを載置し、アーク放電により炭素及び金属をイオン化して、前記処理対象物の表面にダイヤモンドライクカーボン膜（ＤＬＣ膜）を、中間膜を介して製膜する工程を含む。前記ＤＬＣ膜の平均粗さＲａは０．０５μｍ以上である。 A method for manufacturing a flow path switching valve according to the present invention includes: a stator having a plurality of first through holes; a rotor seal rotating in contact with the stator and having a plurality of second through holes; in which the stator and the rotor seal as objects to be treated are placed on an arc ion plating device, and carbon and metal are separated by arc discharge is ionized to form a diamond-like carbon film (DLC film) on the surface of the object to be processed via an intermediate film. The DLC film has an average roughness Ra of 0.05 μm or more.
　本発明に係る流路切替バルブ、及びその製造方法によれば、ステータとロータシールの固着によるステータとロータシールの接触面の摩耗を抑制し、流路切替バルブの長寿命化を図ることができる。 According to the flow path switching valve and the manufacturing method thereof according to the present invention, wear of the contact surface between the stator and the rotor seal due to fixation between the stator and the rotor seal can be suppressed, and the service life of the flow path switching valve can be extended. .
実施の形態に係る流路切替バルブ１の断面図である。1 is a cross-sectional view of a channel switching valve 1 according to an embodiment; FIG. ロータシール１２の上面図である。4 is a top view of the rotor seal 12; FIG. ロータシール１２とロータ１３の接触面の上面図である。3 is a top view of a contact surface between a rotor seal 12 and a rotor 13; FIG. ステータ１１とロータシール１２に成膜されている保護膜１２０（ＤＬＣ膜１２１と中間膜１２２）の断面図である。3 is a cross-sectional view of a protective film 120 (a DLC film 121 and an intermediate film 122) formed on the stator 11 and the rotor seal 12; FIG. アークイオンプレーティング法による四面体アモルファスカーボンのＤＬＣ膜１２１の成膜方法を説明する。A method of forming the DLC film 121 of tetrahedral amorphous carbon by the arc ion plating method will be described. 図１の流路切替バルブ１を搭載した液体クロマトグラフ４２１の流路模式図である。FIG. 2 is a flow path schematic diagram of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1. FIG. 図１の流路切替バルブ１を搭載した液体クロマトグラフ４２１の流路模式図である。FIG. 2 is a flow path schematic diagram of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1. FIG. 図１の流路切替バルブ１の慣らし運転時における回転トルクの変化のグラフの一例である。FIG. 2 is an example of a graph of changes in rotational torque during pre-running of the flow path switching valve 1 of FIG. 1. FIG. ステータ１１とロータシール１２の往復運動を行った場合における傷の延伸について説明する概略図である。FIG. 5 is a schematic diagram for explaining extension of a scratch when a stator 11 and a rotor seal 12 reciprocate; ステータ１１とロータシール１２の往復運動を行った場合における傷の延伸について説明する概略図である。FIG. 5 is a schematic diagram for explaining extension of a scratch when a stator 11 and a rotor seal 12 reciprocate; ＤＬＣ膜１２１の膜厚、硬度と流路切替バルブ１の寿命の関係を示す。3 shows the relationship between the film thickness and hardness of the DLC film 121 and the service life of the channel switching valve 1. FIG. 図７に図４Ａのロータシール流路の端部の断面写真を示す。FIG. 7 shows a cross-sectional photograph of the end portion of the rotor seal channel of FIG. 4A. 本実施の形態に従うサンプル１～３についての、慣らし運転の前後でのステータ側粗さＲａ１、シール側粗さＲａ２の変化と、流路切替バルブ１の寿命（使用可能回数）を示す。4 shows changes in stator-side roughness Ra1 and seal-side roughness Ra2 before and after running-in, and the service life (usable number of times) of flow path switching valve 1 for samples 1 to 3 according to the present embodiment.
　以下、添付図面を参照して本実施形態について説明する。添付図面では、機能的に同じ要素は同じ番号で表示される場合もある。なお、添付図面は本開示の原理に則った実施形態と実装例を示しているが、これらは本開示の理解のためのものであり、決して本開示を限定的に解釈するために用いられるものではない。本明細書の記述は典型的な例示に過ぎず、本開示の特許請求の範囲又は適用例を如何なる意味においても限定するものではない。 The present embodiment will be described below with reference to the accompanying drawings. In the accompanying drawings, functionally identical elements may be labeled with the same numbers. It should be noted that although the attached drawings show embodiments and implementation examples in accordance with the principles of the present disclosure, they are for the purpose of understanding the present disclosure and are in no way used to interpret the present disclosure in a restrictive manner. isn't it. The description herein is merely exemplary and is not intended to limit the scope or application of this disclosure in any way.
　本実施形態では、当業者が本開示を実施するのに十分詳細にその説明がなされているが、他の実装・形態も可能で、本開示の技術的思想の範囲と精神を逸脱することなく構成・構造の変更や多様な要素の置き換えが可能であることを理解する必要がある。従って、以降の記述をこれに限定して解釈してはならない。 Although the present embodiments are described in sufficient detail to enable those skilled in the art to practice the present disclosure, other implementations and configurations are possible without departing from the scope and spirit of the present disclosure. It is necessary to understand that it is possible to change the composition/structure and replace various elements. Therefore, the following description should not be construed as being limited to this.
　図１を参照して、実施の形態に係る流路切替バルブ１の構造を説明する。図１Ａは、実施の形態に係る流路切替バルブ１の断面図であり（図１Ｃの破線１９の断面図）、図１Ｂはロータシール１２の上面図である。また、図１Ｃは、ロータシール１２とロータ１３の接触面の上面図である。また、図１Ｄは、ステータ１１とロータシール１２に成膜されている保護膜１２０（ＤＬＣ膜１２１と中間膜１２２）の断面図である。 The structure of the flow path switching valve 1 according to the embodiment will be described with reference to FIG. FIG. 1A is a cross-sectional view of the flow path switching valve 1 according to the embodiment (cross-sectional view taken along dashed line 19 in FIG. 1C), and FIG. 1B is a top view of the rotor seal 12. FIG. 1C is a top view of the contact surface between the rotor seal 12 and the rotor 13. FIG. FIG. 1D is a cross-sectional view of protective film 120 (DLC film 121 and intermediate film 122) formed on stator 11 and rotor seal 12. As shown in FIG.
　図１Ａに示すように、流路切替バルブ１は、ステータ１１、ロータシール１２、ロータ１３、及びハウジング１５から構成される。 As shown in FIG. 1A, the flow path switching valve 1 is composed of a stator 11, a rotor seal 12, a rotor 13, and a housing 15.
　ステータ１１は、例えばステンレス（以下ＳＵＳ３１６）などの金属やセラミックを材料として構成される本体部を有し、その本体部を貫通するように形成される複数のステータ流路１１１～１１６を備えている（図１Ｃ参照）ステータ流路１１１～１１６の端部は、ステータ１１において、ロータ１３の回転軸を中心とした一の円周上に配置される。これらのステータ流路１１１～１１６に、図示しない配管が接続される。 The stator 11 has a main body made of metal such as stainless steel (SUS316, hereinafter) or ceramic, and has a plurality of stator flow paths 111 to 116 formed so as to pass through the main body. (See FIG. 1C) The ends of the stator flow paths 111 to 116 are arranged on one circumference around the rotation axis of the rotor 13 in the stator 11 . Pipes (not shown) are connected to these stator flow paths 111-116.
　ロータシール１２は、ＳＵＳ３１６など金属、セラミック、樹脂等を材料として構成される本体部を有し、その本体部は、円弧状に略等間隔に形成された複数（図１Ｂに図示の例では３つ）のロータシール流路１３１、１３２、１３３を有する。摺動面を形成するステータ１１とロータシール１２の表面には、耐摩耗性能を向上させるための保護膜１２０がコーティングされている。保護膜１２０は、耐摩耗性能を持たせるためＤＬＣ膜１２１、及び中間膜１２２で構成される（図１Ｄ参照）。 The rotor seal 12 has a main body made of metal such as SUS316, ceramic, resin, or the like. ) rotor seal passages 131 , 132 , 133 . The surfaces of the stator 11 and the rotor seal 12 forming sliding surfaces are coated with a protective film 120 for improving wear resistance performance. The protective film 120 is composed of a DLC film 121 and an intermediate film 122 to provide abrasion resistance (see FIG. 1D).
　ロータシール１２は、ロータ１３のバネ（図示せず）によりステ－タ１１に押しつけられている。ステータ１１とロータシール１２とが接触し、所定の角度関係に調整されると、図１Ｃのように、例えばロータシール流路１３１及びステータ流路１１１、１１２が連結して形成される流路、ロータシール流路１３２及びステータ流路１１３、１１４が連結して形成される流路、及び、ロータシール流路１３３及びステータ流路１１５、１１６が連結して形成される流路が形成される。ロータ１３が更に回転すると、別の流路が形成され得る（詳しくは後述する）。これらの流路の間での液漏れ、及び外部への液漏れを防止するため、保護膜１２０が設けられ、バネによる押下がされることで、液密性が維持されている。 The rotor seal 12 is pressed against the stator 11 by a spring (not shown) of the rotor 13. When the stator 11 and the rotor seal 12 come into contact with each other and are adjusted to have a predetermined angular relationship, as shown in FIG. A flow path formed by connecting the rotor seal flow path 132 and the stator flow paths 113 and 114 and a flow path formed by connecting the rotor seal flow path 133 and the stator flow paths 115 and 116 are formed. Further rotation of the rotor 13 may create another flow path (described in detail below). A protective film 120 is provided in order to prevent liquid leakage between these channels and liquid leakage to the outside.
　ロータシール１２は、ピン１６、１７によりロータ１３に固定される。ロータシール１２は、ロータ１３に接続されたモータ（図示せず）により、ステータ１１に対し摺動しつつ回転する。ロータ１３の回転角度は、例えば、モータにエンコーダ（図示せず）を備えることで計測され得る。 The rotor seal 12 is fixed to the rotor 13 by pins 16 and 17. The rotor seal 12 rotates while sliding relative to the stator 11 by a motor (not shown) connected to the rotor 13 . The rotation angle of the rotor 13 can be measured, for example, by equipping the motor with an encoder (not shown).
　ロータシール１２とステータ１１の摺動面に成膜された保護膜１２０について、図１Ｄを参照して説明する。保護膜１２０は一例として、ＳＵＳ３１６の基材１２３（ステータ１１とロータシール１２の本体部）に形成される中間膜１２２と、その中間膜１２２の上に形成されるダイヤモンドライクカーボン膜（ＤＬＣ膜）１２１を備える。ステータ１１とロータシール１２との接触面である両者の最表面にＤＬＣ膜１２１が成膜され、ＤＬＣ膜１２１同士が互いに摺動するようステータ１１とロータシール１２が配置される。 The protective film 120 formed on the sliding surfaces of the rotor seal 12 and the stator 11 will be described with reference to FIG. 1D. As an example of the protective film 120, an intermediate film 122 formed on a base material 123 of SUS316 (the main body of the stator 11 and the rotor seal 12) and a diamond-like carbon film (DLC film) formed on the intermediate film 122. 121. A DLC film 121 is formed on the outermost surfaces of the stator 11 and the rotor seal 12, which are the contact surfaces of the stator 11 and the rotor seal 12, and the stator 11 and the rotor seal 12 are arranged so that the DLC films 121 slide against each other.
　ＤＬＣ膜１２１及び中間膜１２２は、アークイオンプレーティング法と呼ばれる技術によって形成することができる。アークイオンプレーティング法により、ＤＬＣ膜１２１には四面体アモルファスカーボンのＤＬＣが成膜される。四面体アモルファスカーボンは水素イオンを含まないＤＬＣである。水素イオンを含まない四面体アモルファスカーボンのＤＬＣ膜を採用することにより、リンギングを回避しつつ寿命が長い流路切替バルブを提供することが可能になる。 The DLC film 121 and intermediate film 122 can be formed by a technique called arc ion plating. A DLC of tetrahedral amorphous carbon is formed on the DLC film 121 by an arc ion plating method. Tetrahedral amorphous carbon is DLC that does not contain hydrogen ions. By adopting a tetrahedral amorphous carbon DLC film that does not contain hydrogen ions, it is possible to provide a channel switching valve that has a long life while avoiding ringing.
　アークイオンプレーティング法による四面体アモルファスカーボンのＤＬＣ膜１２１の成膜方法を図２を参照して説明する。図２は、アークイオンプレーティング法を実行可能なアークイオンプレーティング装置３００の概略構成の一例を示している。 A method for forming the tetrahedral amorphous carbon DLC film 121 by the arc ion plating method will be described with reference to FIG. FIG. 2 shows an example of a schematic configuration of an arc ion plating apparatus 300 capable of executing the arc ion plating method.
　アークイオンプレーティング装置３００は、一例として、真空チャンバ３０１を備え、真空チャンバ３０１は処理対象物３１０を保持するための回転テーブル３１１を備える。真空チャンバ３０１は更に、ＤＬＣ膜１２１の元となるグラファイト陰極のカソード３０２と、中間膜１２２を形成するために使用する金属ターゲット３０３とを備える。中間膜１２２は、主にアルミニウム、クロム、チタン、タングステンなどの金属で形成される。金属ターゲット３０３の材料は、ステータ１１やロータシール１２の材料に応じて変更することができる。 The arc ion plating apparatus 300 includes, as an example, a vacuum chamber 301, and the vacuum chamber 301 includes a rotary table 311 for holding an object 310 to be processed. The vacuum chamber 301 further comprises a graphite cathode 302 from which the DLC film 121 is formed, and a metal target 303 used to form the intermediate film 122 . The intermediate film 122 is mainly made of metal such as aluminum, chromium, titanium, and tungsten. The material of the metal target 303 can be changed according to the material of the stator 11 and rotor seal 12. FIG.
　真空チャンバ３０１は更に、アルゴンガス３０１１を注入するガス注入ポート３０１２、及び、真空引き３０１３を行う真空引きポート３０１４を備える。処理対象物３１０（ステータ１１やロータシール１２に相当）は、回転テーブル３１１の上に配置され、回転テーブル３１１はバイアス電源３１２に接続される。処理対象物３１０は、回転テーブル３１１を介してバイアス電源３１２に電気的に接続される。これにより、バイアス電源３１２は、処理対象物３１０にバイアス電圧を印加することができる。 The vacuum chamber 301 further includes a gas injection port 3012 for injecting argon gas 3011 and an evacuation port 3014 for evacuation 3013 . A workpiece 310 (corresponding to the stator 11 and rotor seal 12 ) is placed on a rotary table 311 , and the rotary table 311 is connected to a bias power supply 312 . A processing object 310 is electrically connected to a bias power supply 312 via a rotary table 311 . Thereby, the bias power supply 312 can apply a bias voltage to the processing object 310 .
　ＤＬＣ膜１２１と中間膜１２２の成膜プロセスについて説明する。真空チャンバ３０１中にアルゴンガス３０１１を充満させる。その後、アーク放電発生装置（図示せず）によりアーク放電を実行することでグラファイト陰極のカソード３０２と金属ターゲット３０３の炭素や金属をイオン化し、バイアス電源３１２を用いて、ＤＬＣや金属イオンを処理対象物３１０の最表面に引き込む。これにより、処理対象物３１０にＤＬＣ膜１２１及び中間膜１２２が形成される。アークイオンプレーティング法ではドロップレットと呼ばれるＤＬＣの塊が含まれて成膜されるため、ＤＬＣ膜１２１は、その垂直方向の平均粗さＲａが、後述する慣らし運転前の段階において０．０５μｍ以上０．３μｍ以下に形成される。ステータ１１のＤＬＣ膜１２１の平均粗さＲａ１（ステータ側粗さＲａ１）、ロータシール１２のＤＬＣ膜１２１の平均粗さＲａ２（シール側粗さＲａ２）のいずれも０．０５μｍ以上０．３μｍ以下とするのが好適である。ただし、平均粗さＲａ２の値が、平均粗さＲａ１よりも大きい値とすることが好適である。Ｒａ２＞Ｒａ１とすることで、よりステータ１１とロータシール１２との間の固着が一層発生し難くなる。 A film forming process for the DLC film 121 and the intermediate film 122 will be described. Argon gas 3011 is filled in the vacuum chamber 301 . After that, arc discharge is performed by an arc discharge generator (not shown) to ionize the carbon and metal of the cathode 302 of the graphite cathode and the metal target 303, and using the bias power supply 312, DLC and metal ions are processed. It pulls to the outermost surface of the object 310 . Thereby, the DLC film 121 and the intermediate film 122 are formed on the object 310 to be processed. In the arc ion plating method, DLC masses called droplets are included in the film, so the DLC film 121 has an average vertical roughness Ra of 0.05 μm or more in the stage before the break-in operation described later. It is formed to 0.3 μm or less. Both the average roughness Ra1 of the DLC film 121 of the stator 11 (stator-side roughness Ra1) and the average roughness Ra2 of the DLC film 121 of the rotor seal 12 (seal-side roughness Ra2) are 0.05 μm or more and 0.3 μm or less. It is preferred to However, it is preferable that the value of the average roughness Ra2 be set to a value larger than the average roughness Ra1. By setting Ra2>Ra1, sticking between the stator 11 and the rotor seal 12 is more difficult to occur.
　流路切替バルブ１のＤＬＣ膜１２１は、２０ＧＰａ～６０ＧＰａの硬度を有する。その硬度は、プロセス中にバイアス電源３１２のバイアス電圧を調整することにより得ることができる。 The DLC film 121 of the channel switching valve 1 has a hardness of 20 GPa to 60 GPa. The hardness can be obtained by adjusting the bias voltage of bias power supply 312 during the process.
　図１Ａの流路切替バルブ１を搭載した液体クロマトグラフ４２１の流路模式図を図３Ａ、図３Ｂに示す。図３Ａは、ある回転角度において得られる流路の模式図であり、図３Ｂは、図３Ａの状態から約６０度ロータ１３を回転した状態での流路の模式図である。 FIGS. 3A and 3B show schematic flow path diagrams of a liquid chromatograph 421 equipped with the flow path switching valve 1 of FIG. 1A. 3A is a schematic diagram of the flow path obtained at a certain rotation angle, and FIG. 3B is a schematic diagram of the flow path when the rotor 13 is rotated about 60 degrees from the state of FIG. 3A.
　液体クロマトグラフ４２１は、送液ポンプ４２２、ニードル４２３、シリンジポンプ４２４、流路切替バルブ１、分離カラム４２６、検出器４２７、配管Ｐ２、及びそれらを接続する配管Ｐ１から構成される。流路切替バルブ１のステータ流路１１１、１１２、１１３、１１４、１１５、１１６は、送液ポンプ４２２、分離カラム４２６、ニードル４２３、シリンジポンプ４２４、又は配管Ｐ２に接続されている。 The liquid chromatograph 421 is composed of a liquid feed pump 422, a needle 423, a syringe pump 424, a channel switching valve 1, a separation column 426, a detector 427, a pipe P2, and a pipe P1 connecting them. The stator channels 111, 112, 113, 114, 115, and 116 of the channel switching valve 1 are connected to the liquid feed pump 422, the separation column 426, the needle 423, the syringe pump 424, or the pipe P2.
　ロータ１３が回転し、図３Ａの状態になると、送液ポンプ４２２により送液される溶離液４２９が、ステータ流路１１１、ロータシール流路１３１、ステータ流路１１２、配管Ｐ２、ステータ流路１１５、ロータシール流路１３３、ステータ流路１１６を通って、分離カラム４２６に導入され、更に、検出器４２７、廃液タンク４８１に流れる状態が得られる。 When the rotor 13 rotates and enters the state of FIG. , the rotor seal flow path 133 and the stator flow path 116 , the separation column 426 , the detector 427 and the waste liquid tank 481 .
　また、図３Ａの状態では、ニードル４２３がステータ流路１１３に接続され、シリンジポンプ４２４がステータ流路１１４に接続され、ステータ流路１１３、ロータシール流路１３２、ステータ流路１１４、シリンジポンプ４２４が接続された状態が得られる。 3A, the needle 423 is connected to the stator flow path 113, the syringe pump 424 is connected to the stator flow path 114, and the stator flow path 113, rotor seal flow path 132, stator flow path 114, and syringe pump 424 are connected. is connected.
　その後、図３Ａの状態から、流路切替バルブ１を図３Ａの摺動方向２１１に６０度回転させて流路を切り替えると、図３Ｂの状態が得られる。図３Ｂの状態では、サンプルＳＰが、シリンジポンプ４２４の吸引により、ニードル４２３、ステータ流路１１３、ロータシール流路１３１、ステータ流路１１２、配管Ｐ２、ステータ流路１１５、ロータシール流路１３２、ステータ流路１１４へと吸引される状態が得られる。また、送液ポンプ４２２により送液される溶離液４２９が、ステータ流路１１１、ロータシール流路１３３、ステータ流路１１６を通って、分離カラム４２６、検出器４２７を通って廃液タンク４８１に流れる状態が得られる。 After that, from the state of FIG. 3A, the flow path switching valve 1 is rotated 60 degrees in the sliding direction 211 of FIG. 3A to switch the flow path, and the state of FIG. 3B is obtained. In the state of FIG. 3B, the sample SP is sucked by the syringe pump 424, and the needle 423, the stator flow channel 113, the rotor seal flow channel 131, the stator flow channel 112, the pipe P2, the stator flow channel 115, the rotor seal flow channel 132, A state of being sucked into the stator flow path 114 is obtained. Also, the eluent 429 sent by the liquid-sending pump 422 passes through the stator channel 111, the rotor seal channel 133, the stator channel 116, the separation column 426, the detector 427, and flows into the waste liquid tank 481. status is obtained.
　図３Ｂの状態から、流路切替バルブ１を時計回りの摺動方向２１２に６０度回転させると、流路切替バルブ１は図３Ａの状態に戻ることができる。図３Ａの状態で、送液ポンプ４２２を駆動して、ステータ流路１１１、ロータシール流路１３１、ステータ流路１１２へと溶離液４２９を送液することにより、配管Ｐ２内にあるサンプルＳＰを分離カラム４２６に送液することができる。サンプルＳＰは、分離カラム４２６で分離された後、検出器４２７で検出される。検出動作の終了後、全体の流路を洗浄するため更に数秒溶離液の送液を継続する。その後、別のサンプルの分析のために図３Ｂの状態に戻す。以後、図３Ａ、図３Ｂの状態を設定し、上記の動作を繰り返すことにより、サンプルＳＰの検査が継続される。 When the flow path switching valve 1 is rotated clockwise by 60 degrees in the sliding direction 212 from the state of FIG. 3B, the flow path switching valve 1 can return to the state of FIG. 3A. In the state of FIG. 3A, the liquid-sending pump 422 is driven to send the eluent 429 to the stator channel 111, the rotor seal channel 131, and the stator channel 112, thereby removing the sample SP in the pipe P2. It can be sent to separation column 426 . The sample SP is detected by the detector 427 after being separated by the separation column 426 . After the detection operation is completed, the eluent is continued to be supplied for several seconds to wash the entire channel. Then return to the state of FIG. 3B for analysis of another sample. After that, by setting the states shown in FIGS. 3A and 3B and repeating the above operation, the inspection of the sample SP is continued.
　分離カラム４２６は、内部に数マイクロメートルの粒子が充填されていて流体抵抗が大きい。また、分離カラム４２６のサンプル分離性能を向上させるため、分離カラム４２６に接続される配管Ｐ１の流路径は０．１ｍｍ程度に設計されており、同様に流体抵抗が大きい。そのため、送液ポンプ４２２は数十ＭＰａの高い圧力で溶離液４２９を送液するよう構成されている。一方、シリンジポンプ４２４には流路抵抗の大きい配管等は接続されていないので、シリンジポンプ４２４の送液圧力は大気圧（０．１ＭＰａ）に近い値に設定される。液体クロマトグラフの用途によっては、ポンプからは３０～１２０ＭＰａ、又はそれを超える圧力の液体が送液されており、この高圧条件下でバルブは動作しなければならない。このように高圧送液下で、ステータ１１とロータシール１２の接触面にシール性を持たせるために、ステータ１１とロータシール１２を大きな力で押し付ける必要がある。使用する液圧に合わせて、ステータ１１とロータシール１２の接触面の面圧が約６０～１５０ＭＰａとなるよう流路切替バルブが構成される。 The separation column 426 is filled with particles of several micrometers inside and has high fluid resistance. Further, in order to improve the sample separation performance of the separation column 426, the flow path diameter of the pipe P1 connected to the separation column 426 is designed to be approximately 0.1 mm, which similarly has large fluid resistance. Therefore, the liquid-sending pump 422 is configured to send the eluent 429 at a high pressure of several tens of MPa. On the other hand, since the syringe pump 424 is not connected to a pipe or the like having a large flow resistance, the liquid feeding pressure of the syringe pump 424 is set to a value close to the atmospheric pressure (0.1 MPa). Depending on the application of the liquid chromatograph, the liquid is delivered from the pump at a pressure of 30 to 120 MPa or more, and the valve must operate under this high pressure condition. In order to provide the contact surfaces of the stator 11 and the rotor seal 12 with sealing properties under high-pressure liquid feeding, it is necessary to press the stator 11 and the rotor seal 12 with a large force. The flow path switching valve is configured so that the surface pressure of the contact surface between the stator 11 and the rotor seal 12 is about 60 to 150 MPa according to the hydraulic pressure used.
　このようにステータ１１とロータシール１２の接触面の面圧が大きい場合において、ステータ１１とロータシール１２のそれぞれの最表面の粗さＲａが、例えば０．０２５μｍ以下のような鏡面に近い値とされると、ステータ１１とロータシール１２がリンギング現象とよばれる分子間結合による固着を起こすことがある。この場合、流路切替バルブ１が動作しなくなる可能性がある。 When the surface pressure of the contact surface between the stator 11 and the rotor seal 12 is large as described above, the roughness Ra of the outermost surface of each of the stator 11 and the rotor seal 12 is a value close to a mirror surface such as 0.025 μm or less, for example. As a result, the stator 11 and the rotor seal 12 may stick due to intermolecular bonds called ringing phenomenon. In this case, the channel switching valve 1 may not operate.
　そこで、本実施の形態の流路切替バルブ１は、アークイオンプレーティング法により、ステータ１１とロータシール１２の最表層に、保護膜１２０の一部としてＤＬＣ膜１２１を備えている。ＤＬＣ膜１２１の、後述する慣らし運転前における最表面の平均粗さＲａは０．０５μｍ以上で、例えば０．０５～０．１５μｍとされる。このため、ステータ１１とロータシール１２の固着は効果的に抑止される。これによりステータ１１とロータシール１２の接触面で、異常摩耗や焼き付きなども発生せず、長寿命な流路切替バルブ１を提供することができる。 Therefore, the flow path switching valve 1 of the present embodiment includes a DLC film 121 as part of the protective film 120 on the outermost layers of the stator 11 and rotor seal 12 by arc ion plating. The DLC film 121 has an outermost surface average roughness Ra of 0.05 μm or more, for example, 0.05 to 0.15 μm, before running-in, which will be described later. This effectively prevents the stator 11 and rotor seal 12 from sticking together. As a result, the contact surface between the stator 11 and the rotor seal 12 does not suffer from abnormal wear or seizure, and a long-life passage switching valve 1 can be provided.
　また、本実施の形態の流路切替バルブ１は、ステータ１１とロータシール１２を接触させたのち、ロータ１３を反時計回り摺動方向２１１、及び時計回り摺動方向２１２へと繰り返し回転させて慣らし運転を実行する。慣らし運転は、溶離液４２９を送液しながら、摺動方向２１１、摺動方向２１２に１００－３０００回程度ロータ１３を回転（往復運動）させるものである。これにより、ＤＬＣ膜１２１の最表面が適宜平滑化され、平均粗さＲａが減少しつつも、かつステータ１１とロータシール１２が固着しない平均粗さとされる。すなわち、ステータ１１とロータシール１２が接触面で固着せず、長寿命なバルブを提供することができる。 Further, in the flow path switching valve 1 of the present embodiment, after the stator 11 and the rotor seal 12 are brought into contact with each other, the rotor 13 is repeatedly rotated in the counterclockwise sliding direction 211 and the clockwise sliding direction 212. Perform a running-in. The break-in operation is to rotate (reciprocate) the rotor 13 about 100 to 3000 times in the sliding directions 211 and 212 while feeding the eluent 429 . As a result, the outermost surface of the DLC film 121 is properly smoothed, and the average roughness Ra is reduced, and the stator 11 and the rotor seal 12 are not stuck to each other. That is, the stator 11 and the rotor seal 12 do not stick together at their contact surfaces, and a long-life valve can be provided.
　慣らし運転に当たっては、図４に示すように、ロータ１３を回転させる駆動装置の回転トルクを監視することが好適である。慣らし運転の開始直後は、大きな平均粗さに基づく静止摩擦係数の関係で大きな回転トルクが発生するが、その後は回転トルクは低下し、以後平均粗さの低下により、回転トルクも徐々に低下する。この回転トルクを監視することで、適切な平均粗さを得ることができる。 During break-in, it is preferable to monitor the rotational torque of the driving device that rotates the rotor 13, as shown in FIG. Immediately after the start of break-in, a large rotational torque is generated due to the static friction coefficient based on the large average roughness. . An appropriate average roughness can be obtained by monitoring this rotational torque.
　また、３０～１２０ＭＰａの高圧送液条件下で高圧流路と低圧流路を切替える場合に発生するキャビテーション（空洞現象）により、ステータ１１とロータシール１２の接触面が摩耗し、両者間のシール性が保たれず、バルブ寿命が短くなる可能性がある。このキャビテーションによる接触面の摩耗箇所について図４を参照して説明する。 In addition, due to cavitation (cavitation phenomenon) that occurs when switching between the high-pressure flow path and the low-pressure flow path under high-pressure liquid feeding conditions of 30 to 120 MPa, the contact surface between the stator 11 and the rotor seal 12 wears, and the sealing performance between the two is reduced. is not maintained and the valve life may be shortened. Abraded portions of the contact surface due to this cavitation will be described with reference to FIG.
　ロータ１３が回転し、図３Ｂの状態から、図３Ａの状態へと切り替えがされる場合を考える。このとき、図３Ｂの状態において低圧のシリンジポンプ４２４につながるロータシール流路１３１は、図３Ａの状態においては、高圧の送液ポンプ４２２とステータ流路１１１を介して接続される。この場合、ステータ流路１１１とロータシール流路１３１の圧力差が大きいため、その圧力により、キャビテーションがステータ流路１１１及びロータシール流路１３１内に発生する。その後、送液ポンプ４２２から高圧の流体が流れるため、キャビテーションが流路内で崩壊する。キャビテーションが崩壊する際に、ステータ１１とロータシール１２の流路内で、衝撃圧や高速の流れが生じ、ステータ流路１１１とロータシール流路１３１の流路端部に摩耗が起きる。図５Ａ、図５Ｂにキャビテーションによってできる流路端部の傷の一例を模式的に示す。ステータ流路１１１にはステータ流路端部の傷１１１１、ロータシール流路１３１にはロータシール流路端部の傷１３１１ができる。 Consider a case where the rotor 13 rotates and the state in FIG. 3B is switched to the state in FIG. 3A. At this time, the rotor seal channel 131 connected to the low-pressure syringe pump 424 in the state of FIG. 3B is connected to the high-pressure liquid feed pump 422 via the stator channel 111 in the state of FIG. 3A. In this case, since the pressure difference between the stator flow path 111 and the rotor seal flow path 131 is large, cavitation occurs in the stator flow path 111 and the rotor seal flow path 131 due to the pressure. After that, high-pressure fluid flows from the liquid-sending pump 422, so that the cavitation collapses in the flow path. When the cavitation collapses, impact pressure and high-speed flow are generated in the flow paths of the stator 11 and the rotor seal 12 , and wear occurs at the flow path ends of the stator flow path 111 and the rotor seal flow path 131 . FIG. 5A and FIG. 5B schematically show an example of flaws at the ends of the flow path caused by cavitation. The stator flow path 111 has a stator flow path end flaw 1111 , and the rotor seal flow path 131 has a rotor seal flow path end flaw 1311 .
　図３Ａ、図３Ｂに示した往復運動の回数が増えると、ステータ流路端部の傷１１１１が方向１１１２（図５Ａ）に延伸し、ロータシール流路端部の傷１３１１は方向１３１２（図５Ｂ）に延伸する。そして最終的に、図５Ｂで示すように、高圧のロータシール流路１３３、ステータ流路１１１、ステータ流路の傷１１１１と、低圧のロータシール流路の傷１３１１と、ロータシール流路１３１が接続して、シール性が保たれず、液漏れが発生する虞が高まる。 As the number of reciprocating motions shown in FIGS. 3A and 3B increases, stator channel end flaws 1111 extend in direction 1112 (FIG. 5A) and rotor seal channel end flaws 1311 extend in direction 1312 (FIG. 5B). ). Finally, as shown in FIG. 5B, the high-pressure rotor seal flow path 133, the stator flow path 111, the stator flow path flaw 1111, the low-pressure rotor seal flow path flaw 1311, and the rotor seal flow path 131 are formed. If it is connected, the sealing property cannot be maintained, and the risk of liquid leakage increases.
　このキャビテーションによるステータ流路端部の傷１１１１、及びロータシール流路端部の傷１３１１の延伸度は、ステータ１１やロータシール１２に成膜されるＤＬＣ膜１２１の膜厚や硬度により、異なることが判明した。ＤＬＣ膜１２１の膜厚や硬度を考慮することで、キャビテーションによる摩耗に耐え、傷の延伸速度を遅くでき、バルブ寿命を延ばすことができる。 The extension degree of the flaw 1111 at the end of the stator flow path and the flaw 1311 at the end of the rotor seal flow path due to this cavitation varies depending on the thickness and hardness of the DLC film 121 formed on the stator 11 and the rotor seal 12. There was found. By considering the film thickness and hardness of the DLC film 121, it is possible to withstand wear due to cavitation, reduce the stretching speed of scratches, and extend the bulb life.
　図６のグラフにより、ＤＬＣ膜１２１の膜厚、硬度と流路切替バルブ１の寿命の関係を示す。横軸はＤＬＣ膜１２１の膜厚を示し、縦軸は硬度を示し、グラフ中の円の直径は、ある膜厚と硬度のＤＰＣ膜１２１が採用された場合における流路切替バルブ１の寿命を示す。 The graph in FIG. 6 shows the relationship between the film thickness and hardness of the DLC film 121 and the service life of the channel switching valve 1 . The horizontal axis indicates the film thickness of the DLC film 121, the vertical axis indicates the hardness, and the diameter of the circle in the graph indicates the service life of the flow path switching valve 1 when the DPC film 121 having a certain film thickness and hardness is adopted. show.
　本出願の発明者らの検討の結果、アークイオンプレーティング法で成膜したアモルファスカーボンで、硬度２０～６０ＧＰａのＤＬＣ膜を採用すると、バルブ寿命が長くなることが判明した。 As a result of the study by the inventors of the present application, it was found that the valve life is prolonged by adopting a DLC film with a hardness of 20 to 60 GPa, which is amorphous carbon formed by the arc ion plating method.
　硬度２０ＧＰａ未満のＤＬＣ膜１２１が採用された際の寿命５０１は短い。これは、ＤＬＣ膜１２１の硬度が小さいために、キャビテーションによるステータ流路１１１～１１６の端部の傷１１１１、ロータシール流路端部の傷１３１１の延伸速度が速いためと考えられる。 The life 501 is short when the DLC film 121 with a hardness of less than 20 GPa is used. This is presumably because the DLC film 121 has a low hardness, so that cavitation causes the scratches 1111 at the ends of the stator flow paths 111 to 116 and the scratches 1311 at the ends of the rotor seal flow path to extend at a high speed.
　一方、硬度２０～３０ＧＰａのＤＬＣ膜１２１が採用された場合のバルブ寿命５０２は、硬度が２０ＧＰａ以下の場合のバルブ寿命５０１の１．５倍となり、硬度３０～４０ＧＰａのＤＬＣ膜１２１が採用された場合のバルブ寿命５０３は、硬度が２０ＧＰａ以下の場合のバルブ寿命５０１の２倍になり、硬度４０～５０ＧＰａのＤＬＣ膜１２１が採用された場合のバルブ寿命５０４は、硬度が２０ＧＰａ以下の場合のバルブ寿命５０１の７倍となることが判明した。また、５０ＧＰａ～６０ＧＰａのＤＬＣ膜１２１が採用された場合のバルブ寿命５０５は、硬度が２０ＧＰａ以下の場合のバルブ寿命５０１の２倍となることが判明した。 On the other hand, the bulb life 502 when the DLC film 121 with a hardness of 20 to 30 GPa is adopted is 1.5 times the bulb life 501 when the hardness is 20 GPa or less, and the DLC film 121 with a hardness of 30 to 40 GPa is adopted. The valve life 503 when the hardness is 20 GPa or less is double the valve life 501 when the hardness is 20 GPa or less. It turned out to be 7 times the life 501. It was also found that the bulb life 505 when the DLC film 121 of 50 GPa to 60 GPa is adopted is double the bulb life 501 when the hardness is 20 GPa or less.
　他方、硬度が６０ＧＰａを超えるＤＬＣ膜１２１の採用は不適切であることが判明した。６０ＧＰａ超の場合、ステータ１１及びロータシール１２の材料であるＳＵＳ３１６とＤＬＣ膜１２１との硬度差が大きく、ステータ１１とロータシール１２を押し付けた際に、ＤＬＣ膜１２１がステータ１１及びロータシール１２から剥がれ、接触面から液が漏れる虞が高い。 On the other hand, it turned out that the adoption of the DLC film 121 with a hardness exceeding 60 GPa is inappropriate. When it exceeds 60 GPa, the hardness difference between SUS316, which is the material of the stator 11 and the rotor seal 12, and the DLC film 121 is large, and when the stator 11 and the rotor seal 12 are pressed against each other, the DLC film 121 is separated from the stator 11 and the rotor seal 12. There is a high possibility that the liquid will leak from the contact surface due to peeling.
　さらに、ＤＬＣ膜１２１の膜厚に着目すると、膜厚０．５μｍ～１．５μｍが好適であることが判明した。図７に図４Ａのロータシール流路の端部の断面写真の一例を示す。この断面写真は、サンプルを樹脂に包埋して断面を作製し、顕微鏡で撮影した写真である。 Furthermore, focusing on the film thickness of the DLC film 121, it was found that a film thickness of 0.5 μm to 1.5 μm is suitable. FIG. 7 shows an example of a cross-sectional photograph of the end portion of the rotor seal channel of FIG. 4A. This cross-sectional photograph is a photograph of a sample embedded in a resin to prepare a cross section and photographed with a microscope.
　図７に示されるサンプルは、サンプル作製用の樹脂６０３、ＤＬＣ膜１２１、中間膜１２２、ＳＵＳ３１６の基材１２３（ステータ１１又はロータシール１２）を含んでいる。このとき、ＤＬＣ膜１２１の膜厚を１．５μｍより大きくすると、図７に示すように、キャビテーションによる衝撃圧により、中間膜１２２に亀裂６０２ができ、ＤＬＣ膜１２１及び中間膜１２２が、時間経過とともにＳＵＳ３１６の基材１２３から剥がれ、傷として確認される。これにより、ステータ１１とロータシール１２の接触面に隙間が生じ、流路切替バルブ１から液が漏れることが生じ得ることが確認された。 The sample shown in FIG. 7 includes a resin 603 for sample preparation, a DLC film 121, an intermediate film 122, and a base material 123 of SUS316 (stator 11 or rotor seal 12). At this time, if the film thickness of the DLC film 121 is larger than 1.5 μm, as shown in FIG. At the same time, it peels off from the base material 123 of SUS316 and is confirmed as a scratch. As a result, it has been confirmed that a gap may be generated between the contact surfaces of the stator 11 and the rotor seal 12 and the liquid may leak from the flow path switching valve 1 .
　一方で、ＤＬＣ膜１２１の膜厚０．５μｍ未満においては、ステータ１１とロータシール１２を接触させて荷重をかけると、中間膜１２２に亀裂６０２が入り、ＤＬＣ膜１２１及び中間膜１２２がＳＵＳ３１６の基材１２３（ステータとロータシール）から剥離し、流路切替バルブ１から液が漏れることが生じ得ることが確認された。 On the other hand, when the thickness of the DLC film 121 is less than 0.5 μm, when the stator 11 and the rotor seal 12 are brought into contact with each other and a load is applied, cracks 602 are generated in the intermediate film 122, and the DLC film 121 and the intermediate film 122 become SUS316. It has been confirmed that the liquid may peel off from the base material 123 (stator and rotor seal) and leak from the flow path switching valve 1 .
　以上のように、膜厚０．５μｍ～１．５μｍのＤＬＣ膜１２１を保護膜１２０として成膜した流路切替バルブ１は、ステータ１１とロータシール１２の固着やキャビテーションによるステータ１１とロータシール１２の接触面の摩耗を抑制し、流路切替バルブの長寿命化を図ることができることが分かる。以上より、膜厚０．５μｍ～１．５μｍで且つ硬度が２０～６０ＧＰａのＤＬＣ膜１２１の採用が好適である。 As described above, the flow path switching valve 1 formed with the DLC film 121 having a film thickness of 0.5 μm to 1.5 μm as the protective film 120 is capable of preventing the stator 11 and the rotor seal 12 from adhering to each other and cavitation. It can be seen that the wear of the contact surface can be suppressed and the life of the flow path switching valve can be extended. From the above, it is preferable to employ the DLC film 121 having a film thickness of 0.5 μm to 1.5 μm and a hardness of 20 to 60 GPa.
　図８に、本実施の形態に従うサンプル１～３についての、慣らし運転の前後でのステータ側粗さＲａ１、シール側粗さＲａ２の変化と、流路切替バルブ１の寿命（使用可能回数）を示す。図８では、平均粗さＲａ１、Ｒａ２に加え、ステータ１１側のＤＬＣ膜１２１の最大粗さＲｚ１、ロータシール１２側でのＤＬＣ膜１２１の最大粗さＲｚ２の慣らし運転前後での変化も示している。また、各サンプルにおけるＤＬＣ膜１２１の膜厚及び硬度は図８に示す通りである。 FIG. 8 shows changes in the stator-side roughness Ra1 and the seal-side roughness Ra2 before and after the break-in, and the service life (usable number of times) of the flow path switching valve 1 for samples 1 to 3 according to the present embodiment. show. In addition to the average roughnesses Ra1 and Ra2, FIG. 8 also shows changes in the maximum roughness Rz1 of the DLC film 121 on the stator 11 side and the maximum roughness Rz2 of the DLC film 121 on the rotor seal 12 side before and after the break-in. there is Also, the film thickness and hardness of the DLC film 121 in each sample are as shown in FIG.
　図８に示すように、サンプル１～３はいずれも慣らし運転実行前において、ステータ側粗さＲａ１、シール側粗さＲａ２がいずれも０．０５～０．３μｍの範囲に設定されている。実験の結果、いずれのサンプルについても、従来の鏡面状のＤＬＣ膜１２１の寿命を大きく上回る寿命が得られた。 As shown in FIG. 8, for samples 1 to 3, both the stator-side roughness Ra1 and the seal-side roughness Ra2 are set within the range of 0.05 to 0.3 μm before running-in. As a result of the experiment, for any sample, a lifetime greatly exceeding that of the conventional specular DLC film 121 was obtained.
［その他］
　本発明は上記した実施例に限定されるものではなく、様々な変形例が含まれる。例えば、上記した実施例は本発明を分かりやすく説明するために詳細に説明したものであり、必ずしも説明した全ての構成を備えるものに限定されるものではない。また、ある実施例の構成の一部を他の実施例の構成に置き換えることが可能であり、また、ある実施例の構成に他の実施例の構成を加えることも可能である。また、各実施例の構成の一部について、他の構成の追加・削除・置換をすることが可能である。 [others]
The present invention is not limited to the above-described embodiments, and includes various modifications. For example, the above-described embodiments have been described in detail in order to explain the present invention in an easy-to-understand manner, and are not necessarily limited to those having all the described configurations. In addition, it is possible to replace part of the configuration of one embodiment with the configuration of another embodiment, and it is also possible to add the configuration of another embodiment to the configuration of one embodiment. Moreover, it is possible to add, delete, or replace a part of the configuration of each embodiment with another configuration.
１…流路切替バルブ
１１…ステータ
１２…ロータシール
１３…ロータ
１５…ハウジング
１１１、１１２、１１３、１１４、１１５、１１６…ステータ流路
１２０…保護膜
１２１…ＤＬＣ膜
１２２中間膜
１３１、１３２、１３３…ロータシール流路
３００…アークイオンプレーティング装置
３０１…真空チャンバ
３０２…カソード
３０３…金属ターゲット
３１０…処理対象物
３１１…回転テーブル
３１２…バイアス電源
３０１１…アルゴンガス
３０１２…ガス注入ポート
３０１３…真空引き
３０１４…真空引きポート
４２１液体クロマトグラフ
４２２…送液ポンプ
４２３…ニードル
４２４…シリンジポンプ
４２６…分離カラム
４２７…検出器
ＳＰ…サンプル
４２９…溶離液
４８１、４８２…廃液タンク
Ｐ１、Ｐ２…配管 Reference Signs List 1 Flow path switching valve 11 Stator 12 Rotor seal 13 Rotor 15 Housing 111, 112, 113, 114, 115, 116 Stator flow path 120 Protective film 121 DLC film 122 Intermediate films 131, 132, 133 ... Rotor seal channel 300 ... Arc ion plating device 301 ... Vacuum chamber 302 ... Cathode 303 ... Metal target 310 ... Object to be processed 311 ... Rotary table 312 ... Bias power source 3011 ... Argon gas 3012 ... Gas injection port 3013 ... Evacuation 3014 ... Evacuation port 421 Liquid chromatograph 422 ... Liquid sending pump 423 ... Needle 424 ... Syringe pump 426 ... Separation column 427 ... Detector SP ... Sample 429 ... Eluent 481, 482 ... Waste liquid tanks P1, P2 ... Piping

Claims (9)

  1. 　複数の第１の貫通孔を有するステータと、
    　前記ステータと接触しながら回転し複数の第２の貫通孔を有するロータシールと、
    　前記ロータシールを回転させるよう構成されるロータと
    を備え、
    　前記ロータシール及び前記ステータの摺動面にダイヤモンドライクカーボン膜（ＤＬＣ膜）が成膜されており、
    　前記ＤＬＣ膜の平均粗さＲａは０．０５μｍ以上である
    ことを特徴とする流路切替バルブ。     a stator having a plurality of first through holes;
    a rotor seal that rotates in contact with the stator and has a plurality of second through holes;
    a rotor configured to rotate the rotor seal;
    A diamond-like carbon film (DLC film) is formed on sliding surfaces of the rotor seal and the stator,
    The channel switching valve, wherein the DLC film has an average roughness Ra of 0.05 μm or more.
  2. 　前記ＤＬＣ膜の硬度が２０～６０ＧＰａである、請求項１に記載の流路切替バルブ。 The flow path switching valve according to claim 1, wherein the DLC film has a hardness of 20 to 60 GPa.
  3. 　前記ＤＬＣ膜の膜厚が０．５～１．５μｍである、請求項１に記載の流路切替バルブ。 The channel switching valve according to claim 1, wherein the DLC film has a thickness of 0.5 to 1.5 µm.
  4. 　前記ＤＬＣ膜の平均粗さＲａは０．０５μｍ以上０．３μｍ以下である、請求項１に記載の流路切替バルブ。 The flow path switching valve according to claim 1, wherein the DLC film has an average roughness Ra of 0.05 µm or more and 0.3 µm or less.
  5. 　前記ロータシールを、前記ロータによる回転往復運動をすることで慣らし運転を行うように構成された、請求項１に記載の流路切替バルブ。 The flow path switching valve according to claim 1, wherein the rotor seal is configured to perform a break-in operation by rotating the rotor in a reciprocating motion.
  6. 　前記ロータの回転トルクを監視しつつ前記慣らし運転を実行するように構成された、請求項５に記載の流路切替バルブ。 The flow path switching valve according to claim 5, configured to perform the running-in operation while monitoring the rotational torque of the rotor.
  7. 　前記ＤＬＣ膜が、四面体アモルファスカーボンのＤＬＣである、請求項１に記載の流路切替バルブ。 The flow path switching valve according to claim 1, wherein the DLC film is a tetrahedral amorphous carbon DLC.
  8. 　前記ロータシール側のＤＬＣ膜の平均粗さＲａは、前記ステータ側のＤＬＣ膜の平均粗さよりも大きい、請求項１に記載の流路切替バルブ。 The flow path switching valve according to claim 1, wherein the average roughness Ra of the DLC film on the rotor seal side is greater than the average roughness of the DLC film on the stator side.
  9. 　複数の第１の貫通孔を有するステータと、前記ステータと接触しながら回転し複数の第２の貫通孔を有するロータシールと、前記ロータシールを回転させるよう構成されるロータとを備えた流路切替バルブの製造方法において、
    　アークイオンプレーティング装置に、処理対象物としての前記ステータ及び前記ロータシールを載置し、アーク放電により炭素及び金属をイオン化して、前記処理対象物の表面にダイヤモンドライクカーボン膜（ＤＬＣ膜）を、中間膜を介して製膜する工程を含み、　前記ＤＬＣ膜の平均粗さＲａは０．０５μｍ以上である
    ことを特徴とする、流路切替バルブの製造方法。     A flow path comprising a stator having a plurality of first through holes, a rotor seal rotating in contact with the stator and having a plurality of second through holes, and a rotor configured to rotate the rotor seal. In the manufacturing method of the switching valve,
    The stator and the rotor seal as objects to be treated are placed in an arc ion plating apparatus, carbon and metal are ionized by arc discharge, and a diamond-like carbon film (DLC film) is formed on the surface of the object to be treated. 1. A method for manufacturing a flow path switching valve, comprising: forming a film via an intermediate film, wherein the DLC film has an average roughness Ra of 0.05 μm or more.
PCT/JP2022/045270 2022-01-28 2022-12-08 Flow switching valve and manufacturing method therefor WO2023145270A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-011663 2022-01-28
JP2022011663A JP2023110304A (en) 2022-01-28 2022-01-28 Flow passage switching valve, and manufacturing method therefor

Publications (1)

Publication Number Publication Date
WO2023145270A1 true WO2023145270A1 (en) 2023-08-03

Family

ID=87471593

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/045270 WO2023145270A1 (en) 2022-01-28 2022-12-08 Flow switching valve and manufacturing method therefor

Country Status (2)

Country Link
JP (1) JP2023110304A (en)
WO (1) WO2023145270A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08233121A (en) * 1995-02-28 1996-09-10 Kyocera Corp Faucet valve
JP2014520250A (en) * 2011-04-25 2014-08-21 ウオーターズ・テクノロジーズ・コーポレイシヨン Valve with protective coating
JP2014181353A (en) * 2013-03-18 2014-09-29 Shimadzu Corp Arc plasma film deposition apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08233121A (en) * 1995-02-28 1996-09-10 Kyocera Corp Faucet valve
JP2014520250A (en) * 2011-04-25 2014-08-21 ウオーターズ・テクノロジーズ・コーポレイシヨン Valve with protective coating
JP2014181353A (en) * 2013-03-18 2014-09-29 Shimadzu Corp Arc plasma film deposition apparatus

Also Published As

Publication number Publication date
JP2023110304A (en) 2023-08-09

Similar Documents

Publication Publication Date Title
US20100276617A1 (en) Flow channel switching valve
US10428967B2 (en) Valves having protective coatings
EP0791760A2 (en) Water lubricated bearing or water lubricated seal
US9273682B2 (en) Method for making a pump system with enhanced dynamic seal reliability
KR102039532B1 (en) Trunnion ball valve for high pressure, and hydrogen station
US7883093B2 (en) Mechanical seal
CN112204279B (en) Shaft sealing device
JP5343008B2 (en) Ultra-smooth surface sputtering target and method of manufacturing the same
WO2023145270A1 (en) Flow switching valve and manufacturing method therefor
US6234815B1 (en) Rotary joint for fluid
TW201309819A (en) Part with DLC coating and method for applying the DLC coating
US20090029068A1 (en) Carbon thin film manufacturing method and carbon thin film coated body
JP5666583B2 (en) Rotating shear injector valve with coated stator surface
JP4983292B2 (en) Flow path switching valve
JP2918874B1 (en) Mechanical seal and rotary joint for slurry fluid
US9377011B2 (en) High pressure pump with reduced seal wear
JP2004019912A (en) Rotary joint
JP5161931B2 (en) Seal ring for power recovery device for seawater desalination, power recovery device, and seawater desalination device
US20200284384A1 (en) Powder rotary feedthrough having a purge chamber
JP2015523487A (en) Internal combustion engine jacket
CN113463062A (en) Deposition method of diamond-like carbon-based coating on inner wall of bent pipe
US20080178795A1 (en) Gas Bearing Spindles
US20230138338A1 (en) Fluid end with selectively coated surfaces
WO2023217406A1 (en) Amorphous carbon coating for reduction of friction and wear in a slide component
Bloyce Coatings for high performance pumps and compressors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22922562

Country of ref document: EP

Kind code of ref document: A1