• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Optical sensor (100, 400) for measuring at least one dissolved gas in a measuring medium and its production, the sensor comprising a sensor head (102); a shaft element (106) with a recess (110) for a sensitive element (108, 408); and comprises a cylindrical sensor shaft (104) which is arranged between the sensor head (102) and the shaft element (106, 206). The shaft element (106, 206) is characterized by a hydrophilic outer surface (118, 218).
    公开号:CH711881B1
    申请号:CH01563/16
    申请日:2016-11-28
    公开日:2020-06-15
    发明作者:lettow Robert；Ulmer Lilya；Rosa Riccardo
    申请人:Mettler Toledo Gmbh；
    IPC主号:
    专利说明:

    The invention relates to the design and manufacture of an optical sensor for measuring at least one gas dissolved in a measuring medium.
    Optical sensors are based on the fact that a chemical reaction between the sensor material and an analyte, here at least one dissolved gas, in the measuring medium leads to a change in the optical properties of the sensor. A change in the optical properties can, for example, be a change in the absorption or fluorescence properties of a sensitive element arranged in the sensor, so that the reaction can subsequently be detected by spectroscopic methods and thus the analyte content, for example as concentration or partial pressure, in the measuring medium can be determined.
    Optical sensors are used, for example, for measuring gases such as oxygen, ozone and / or carbon dioxide dissolved in the measuring medium in order to determine the gas concentration in the measuring medium, which is given as partial pressure for dissolved gases. When used in biological or biotechnical environments and / or processes, it has been shown that the introduction of gaseous analytes into the process by means of a gas distributor known as an sparger results in gas bubbles which are deposited on the outside of the sensor and thus also on the sensitive element. In the case of a measurement, this then means that the concentration of the analyte in the adhering gas bubbles and not that in the measuring medium is measured by an optical sensor. The gas bubbles in the measuring medium thus lead to incorrect measurements, measuring tips and / or can even lead to an overload of the optical sensor and / or an alarm message if the optical sensor is designed, for example, to measure the low substance concentration of a gas dissolved in the measuring medium and not the measurement of the much higher concentrated gas in the deposited gas bubbles.
    Gaseous analytes, such as oxygen in particular, are introduced with a sparger, for example, into fermentation processes in order to grow higher cell cultures and thus to increase the yield. Gas distributors of different geometries are used as spargers, which are used for introducing gases into process environments or reaction vessels. The sparger is often located on the bottom of the reaction vessel, near the agitator or as a unit with the agitator. In contrast, sensors can be installed at different points in the reaction container. Common installation positions of sensors are from above through the lid or end plate of the reaction vessel or from the side through the wall of the reactor vessel. A sensor is often introduced into the reaction container via a flange located on it, the sensor being introduced into the reaction container either directly or inside a so-called sensor fitting, depending on the configuration. In the case of the fermenter, for example, the sparger introduces oxygen bubbles into the aqueous measuring medium located therein and distributes them throughout the fermenter, more precisely the measuring medium therein, with the aid of the stirrer. These gas bubbles can have different sizes and, as already mentioned, are deposited on the outside of the optical sensor and / or on the sensitive element and cause measuring tips, incorrect measurements and / or even overloads.
    The object of the invention is therefore to provide an optical sensor for measuring dissolved gases in a measuring medium, which largely prevents the accumulation of gas bubbles and thus incorrect measurement and measuring tips.
    [0006] This object is achieved by an optical sensor for measuring at least one dissolved gas in a measuring medium. The optical sensor comprises a sensor head, a shaft element with a recess for a sensitive element and a cylindrical sensor shaft which is arranged between the sensor head and the shaft element. The shaft element is characterized by a hydrophilic outer surface.
    An advantage of an optical sensor according to the invention is that the gas bubbles cannot accumulate and / or roll off on the hydrophilic outer surface. In this way, the measuring performance of the optical sensor can be considerably improved, in particular when measuring gases dissolved in an aqueous measuring medium.
    In an exemplary embodiment, the shaft element also includes a beveled end surface in which the recess for the sensitive element is arranged. The hydrophilic outer surface of the shaft element comprises at least the tapered end surface.
    The design with a beveled end surface is advantageous because the gas bubbles are deflected by the bevel from the end surface and possible accumulation is prevented due to the geometric conditions. The hydrophilic outer surface preferably also comprises at least the parts of the outer surface of the shaft element which are in contact with the measuring medium during operation, in particular the beveled end surface in which the recess for the sensitive element is arranged, which is in direct contact with the operator during operation the measuring medium. Since the shaft element is preferably interchangeable, it is technically feasible to design the entire surface of the shaft element as a hydrophilic outer surface.
    [0010] In an exemplary embodiment, the hydrophilic outer surface of the shaft element has a surface roughness of Ra von 1 μm and preferably of Ra 0.4 0.4 μm. The surface roughness can be determined, for example, with a HOMMEL-ETAMIC T1000 from Jenoptic in accordance with the applicable DIN / ISO standards. The surface roughness can be expressed as a mean roughness Ra in [µm] or as a roughness class. The hydrophilic outer surface preferably has a maximum surface roughness of Ra 1 1 μm or better than roughness class N7 and in particular of Ra 0,4 0.4 μm or better than roughness class N5.
    [0011] The surface roughness of the hydrophilic outer surface also influences its contact angle θ. In a further embodiment, the hydrophilic outer surface of the shaft element has a contact angle of θ 60 60 °, preferably between θ 40 40 ° and θ 55 55 ° and in particular between θ 45 45 ° and θ 50 50 °.
    In a further embodiment, the hydrophilic outer surface of the shaft element has a contact angle θ of θ 60 60 °, preferably between ≥ 10 10 ° and θ 20 20 ° and in particular between θ 12 12 ° and θ 17 17 °.
    The contact angle θ, which can be measured with a contact angle goniometer, for example, indicates the angle between a solid surface and a liquid on the surface, such as water. The contact angle θ depends on the interaction between liquid and solid at the contact limit and indicates the degree of wetting of the surface with the respective liquid. A hydrophobic surface has a high contact angle with water, so that water rolls off a hydrophobic surface. A hydrophilic surface, on the other hand, has a small contact angle so that the water wets this surface without the formation of defined drops, for example. In 1805, Thomas Young defined the contact angle θ of gas-containing liquids on a solid surface as the angle at the phase boundary of the gaseous, liquid and solid phases as γSG = γSL + γLGcosθ with γSG as the interfacial tension between solid and gaseous, γSL as the interfacial tension between solid and liquid, and γLG as the interfacial tension between liquid and gaseous.
    The tapered end surface of the shaft element can have an angle α between 25 and 45 degrees and preferably of approximately 30 degrees. An optical sensor with a shaft element with such a beveled end surface is advantageous since gas bubbles on the one hand cannot even accumulate on the beveled end surface on the one hand and the beveled end surface is not too steep on the other hand, since it has been empirically shown that there is a greater bevel Due to the increased distance between the sensitive element and an at least partially arranged measuring arrangement in the sensor shaft leads to a significant signal loss.
    The shaft element is preferably made of a metal and in particular stainless steel. The shaft element can be designed as a cylindrical hollow body with a beveled end surface. The tapered end surface is arranged at the proximal end of the shaft element and the distal end of the shaft element is designed such that it can be connected to the sensor shaft. The shaft element can be connected fixedly or detachably to the sensor shaft, a detachable connection, such as, for example, a screw, clamp or Bayonet connection, being preferred.
    The terms “distal” and “proximal” are used here in the sense of being removed from the measuring medium during operation (distal) and facing the measuring medium during operation (proximal), the distal end of the shaft element is thus in operation or in the operating position of the Sensor facing away from the measuring medium and its proximal end facing the measuring medium.
    In a further embodiment, the optical sensor further comprises a sensitive element which is arranged in the shaft element and is in contact with the measurement medium during operation of the optical sensor. The sensitive element, also called sensor spot, comprises, for example, a fluorophore, which is sensitive to the at least one dissolved gas to be measured in the measurement medium and is distributed in a carrier. The carrier can be configured, for example, as a polymer disc. If a fluorophore is sensitive to oxygen, for example, its fluorescence spectrum changes upon contact with oxygen, from which the oxygen concentration in the measuring medium can then be determined.
    [0018] In an exemplary embodiment, the optical sensor further comprises a measuring arrangement which comprises optical and electronic components for measuring the at least one dissolved gas in the measuring medium and is arranged in the sensor head and in the sensor shaft. This measuring arrangement includes, among other things, a light source, a light guide, a detector and electronic components for controlling and reading out these optical components. The measurement principle of the optical sensor is based on the fact that light emitted by the light source is guided through the light guide to the sensitive element with shaft element and there interacts with the fluorophore. After interaction with the flurophor, which is arranged in the sensitive element in contact with the measurement medium, the fluorescence signal is passed through the light guide to the detector. The light guide can comprise at least one fiber, several fibers or a fiber bundle.
    A method for producing an optical sensor according to the invention for measuring at least one dissolved gas in a measuring medium, which comprises a sensor head, a shaft element with a recess for a sensitive element and a cylindrical sensor shaft which is arranged between the sensor head and the shaft element, may include the steps of: fabricating a stem member; and creating a hydrophilic outer surface on the shaft element.
    [0020] The hydrophilic outer surface of the shaft element can be produced by one of the following methods: sandblasting, chemical etching, brushing and / or grinding.
    In an exemplary embodiment, the manufacture of the shaft element also includes the creation of a bevelled end surface in which the recess for the sensitive element is arranged. The hydrophilic outer surface is generated at least on the beveled end surface and preferably on all outer surfaces of the shaft element which are in contact with the measuring medium during operation.
    In an exemplary embodiment, the shaft element consists essentially of a metal and in particular of a stainless steel. The surface of these materials can be processed by mechanical or chemical processes so that a hydrophilic outer surface results with defined surface parameters.
    In a further embodiment, the hydrophilic outer surface is generated with a surface roughness of Ra ≤ 1 µm and preferably of Ra ≤ 0.4 µm. The surface roughness Ra can be determined, for example, with a HOMMEL-ETAMIC T1000 from Jenoptic in accordance with the applicable DIN / ISO standards. The surface roughness can be expressed as the mean roughness Ra in [µm] or as the roughness class N. The hydrophilic outer surface is preferably produced with a surface roughness of at most Ra 1 1 μm or less than N7 and in particular with Ra 0,4 0.4 μm or less than N5.
    [0024] The surface roughness of the hydrophilic outer surface also influences the contact angle θ of the hydrophilic outer surface. In a further embodiment, the hydrophilic outer surface of the shaft element is produced with a contact angle of θ 60 60 °, preferably between θ 40 40 ° and θ 55 55 ° and in particular between θ 45 45 ° and θ 50 50 °.
    In a further embodiment, the hydrophilic outer surface of the shaft element has a contact angle θ of θ 60 60 °, preferably between ≥ 10 10 ° and θ 20 20 ° and in particular between θ 12 12 ° and θ 17 17 °.
    A chemical etching process with which the hydrophilic outer surface can be generated with defined surface parameters includes, for example, the introduction of a polished shaft element in hydrochloric acid as an etching reagent with a concentration of [HCl] = 1 mol / L for about 24 h. Other acids, such as nitric acid or aqua regia, can also be used as the etching reagent.
    A hydrophilic outer surface can be mechanically generated on the shaft element, for example by a sandblasting process. For this purpose, the shaft element with an outer surface, which was ground without a center or centerless, is ground as a further surface treatment with corundum. Depending on the grain size of the corundum used, hydrophilic outer surfaces with different surface parameters can be created, as shown in the following table as an example for a shaft element made of stainless steel:<tb> 180 <SEP> 55 - 90 <SEP> N6 <SEP> 0.9<tb> 220 <SEP> 45 - 75 <SEP> N6 <SEP> 0.75<tb> 280 <SEP> 30 - 40 <SEP> N6 <SEP> 0.5<tb> 320 <SEP> 20 - 30 <SEP> N6 <SEP> 0.45<tb> 400 <SEP> 17.3 <SEP> N5 <SEP> 0.35<tb> 500 <SEP> 10-20 <SEP> N5 <SEP> 0.3
    For this purpose, the sheep element at a pressure of 6.0 bar for about 1 min from the inside and outside with a jet distance of about 70-80 mm between the nozzle and the outside diameter of the shaft element, or a jet distance of about 15 mm between the nozzle and the base of the inner diameter, treated with corundum of the appropriate grain size. As already described, the resulting surface roughness is determined with a HUMMEL-ETAMIC T1000 from Jenoptik.
    Various exemplary embodiments of a shaft element according to the invention for an optical sensor are described in more detail below with the aid of the figures, the same elements being provided with the same or similar reference numerals. The figures show:<tb> Fig. 1 <SEP> an exploded view of an optical sensor according to the invention;<tb> Fig. 2 <SEP> a three-dimensional representation of a shaft element of an optical sensor according to the invention;<tb> Fig. 3 <SEP> a section through a shaft element of an optical sensor according to the invention;<tb> Fig. 4 <SEP> a schematic representation of a reaction container with agitator, sparger and an optical sensor according to the invention;<tb> Fig. 5 <SEP> a comparison of the measurement curves of a conventional optical sensor and an optical sensor according to the invention.
    Figure 1 shows an exploded view of an optical sensor 100 according to the invention. The sensor 100 comprises a sensor head 102, a sensor shaft 104 and a shaft element 106. The sensor head 102 has a connection 112 to the sensor 100 with a transmitter, a process control center or to connect another higher-level display and / or evaluation unit. The sensor head 102 is connected proximally to a cylindrical sensor shaft 104. The terms “distal” and “proximal” are used here in the sense of being removed from the measurement medium during operation (distal) and in operation near the measurement medium (proximal). The distal end 102A of the sensor head 102 thus faces away from the measuring medium during operation or in the operating position of the sensor, and the proximal end 102B of the sensor head 102 faces the measuring medium. The length of the sensor shaft 104 can be adjusted during manufacture depending on the area of use and the desired immersion depth of the sensor 100. Optical sensors with total shaft lengths of approx. 120 mm to approx. 600 mm are commercially available. The shaft element 106 is fastened at the end to the sensor shaft 104 or at the proximal end of the sensor shaft 104. This attachment can be released so that the shaft element 106 can be replaced. The shaft element 106 can be detachably attached to the sensor shaft 104, for example by snapping in, screws or a bayonet lock, to name just a few possibilities.
    Furthermore, the optical sensor 100 comprises a measuring arrangement (not shown in detail here) with optical and electronic components which are essentially arranged in the sensor head 102 and in the sensor shaft 104. These components include, among other things, a light source, a light guide 114, which is arranged in the sensor shaft 104 and extends at least to the proximal end 104B of the sensor shaft 104. In addition, these components include means for converting the optical signals into electronic signals and control components for controlling these components.
    The free end of the light guide 114 is in the assembled state of the sensor 100 close behind or even directly on the sensitive element 108, which is in contact with a measuring medium through a recess 110 in the shaft part 106 during operation of the sensor. In operation, light is directed from the light source through the light guide 114 to the sensitive element 108 and after interaction with a fluorophore arranged in the sensitive element to the detector. The fluorophore reacts with an analyte, in particular a dissolved gas, dissolved in the preferably aqueous measurement medium and, after interaction with the light introduced, emits a fluorescence signal which is detected by the detector. The analyte concentration in the measuring medium can then be determined on the basis of the fluorescence signal or a recorded fluorescence spectrum.
    The shaft element 106 has a bevelled end surface 116, in which a recess 110 for a sensitive element 108 is formed. The beveled end surface 116 shown here preferably has an angle α of approximately 30 degrees (see FIG. 3). The chamfering of the end surface 116 was chosen such that an accumulation of gas bubbles is already avoided or at least reduced due to the geometry of the sensor element, and that the end surface 116, on the other hand, has a slope that is as small as possible in order not to lose an unnecessary optical signal, which is otherwise due to this the combination of the light guide 114 and the sensitive element 108 arranged in the beveled surface 116 can occur.
    Furthermore, the shaft element 106 comprises a hydrophilic outer surface 118, which comprises at least the beveled end surface 116 with the recess 110 for the sensitive element 108. The shaft element 106 is preferably a cylindrical hollow body made of a metal and in particular made of stainless steel. The hydrophilic outer surface 116 of the shaft element 106 is produced by one of the following surface treatments: chemical etching processes, sandblasting, brushing or grinding. The surface treatment is preferably checked in such a way that a hydrophilic outer surface 118 with a defined contact angle and / or a defined surface roughness Ra is produced. After the treatment, the hydrophilic outer surface 118 has a contact angle θ of less than θ 60 60 °. Depending on the field of application of the sensor, the hydrophilic outer surface 118 is provided with a contact angle between θ 40 40 ° and θ 55 55 ° and in particular between θ 45 45 ° and θ 50 50 ° or between θ 10 10 ° and θ 20 20 °, in particular between θ ≤ 12 ° and θ ≤ 17 °. After the surface treatment, the hydrophilic outer surface has a surface roughness of Ra ≤ 1 µm or better than N7 and in particular a surface roughness of Ra ≤ 0.4 µm or better than N5.
    Figures 2 and 3 show a shaft element 106, 206 of an optical sensor according to the invention as a three-dimensional representation and in section. The shaft element 106 has a hydrophilic outer surface 118, 218 and a beveled end surface 116 with a recess 110 for a sensitive element 108. The shaft element 206 shown in FIG. 2 comprises a hydrophilic outer surface 218, which only comprises the beveled end surface 116.
    The sensitive element 108 is arranged in the shaft element 106, 206 in such a way that it can come into contact with a measuring medium 416 during operation of the sensor (see FIG. 4). The shaft element 106, 206 is essentially a cylindrical hollow body which is pushed over the end of the sensor shaft 104 facing away from the sensor head 102 and is detachably fastened thereon. The shaft element 106, 206 is interchangeable, since the sensitive element 108 arranged therein, which comprises a fluorophore, is subject to an aging process and can be exchanged if the measurement performance is no longer sufficient.
    FIG. 4 schematically shows a reaction container 414 with built-in stirrer 402, sparger 404 and an optical sensor 400 according to the invention. A measuring medium 416 is arranged in the reaction container 414. Here, the sensor 400 is connected to a higher-level evaluation and / or display unit 410 via a cable 405. The sparger 404 is connected to a gas reservoir 412 via a line 409 with a valve, so that gas bubbles can be introduced into the reaction container 414 and distributed evenly with the stirrer 402. The optical sensor 400 shown in FIG. 4 here comprises a shaft element 406 with a hydrophilic outer surface and a straight end surface, in which there is a recess for a sensitive element 408 at the end.
    FIG. 5 shows a comparison of a measurement curve A of a conventional optical sensor and a measurement curve B of an optical sensor according to the invention. The measurement curves were recorded with a simplified arrangement according to FIG. 4. As the reaction container 416, a beaker was filled with water as the measuring medium 416, both oxygen and nitrogen were introduced into the beaker by means of an saver 404 and distributed in the water by means of an agitator 402. First a conventional sensor with a straight end surface and a polished surface was used and the oxygen content was measured in% air. What is striking about the first part of measurement curve A is the large number of spikes that dominate and falsify the measurement result. After approximately 2600 seconds, the conventional optical sensor was exchanged for an optical sensor 100 according to the invention with a hydrophilic outer surface and a beveled end surface while the measurement was ongoing. Although the second part of the measurement curve B shows a shift in the concentration as a jump in the baseline, since the optical sensor according to the invention was used without calibration, the measurement curve B is essentially constant and smooth and is characterized in particular by the absence of the measurement curve A dominating Spikes out.
    It could thus be shown that by using an optical sensor 100 according to the invention with a shaft element 106 with a hydrophilic outer surface 118 and bevelled end surface 116 measuring tips and incorrect measurements can be avoided and overall a more stable measurement result could be achieved.
    Although the invention has been described by the representation of specific exemplary embodiments, it is obvious that numerous further embodiment variants can be created with knowledge of the present invention, for example by combining the features of the individual exemplary embodiments with one another and / or exchanging individual functional units of the exemplary embodiments . In particular, in addition to the surface treatment processes mentioned, other processes suitable for metal or stainless steel can be used to produce a hydrophilic outer surface. The contact angle and / or the roughness of the hydrophilic outer surface can also be adapted to the process conditions, such as the Sparger gas used, the bubble size and / or the measuring medium. Furthermore, the bevel of the end surface can be varied in order to optimally adapt the shaft element and thus the optical sensor to the conditions in a reaction container.
    List of reference numbers
    100, 400 optical sensor 102 sensor head 102A distal end of sensor head 102 102B proximal end of sensor head 102 104 sensor shaft 104B proximal end of sensor shaft 104 106, 206, 406 shaft element 106A distal end of shaft element 106 106B proximal end of shaft element 106 108, 408 Sensitive element 110 Cut-out in the shaft element 106 112 Connection 114 Light guide 116 Tapered end surface 118, 218 Hydrophilic outer surface 402 Agitator 404 Sparger 405 Line 409 Line 410 Evaluation and / or display unit 412 Gas reservoir 414 Reaction container 416 Measuring medium
    权利要求:
    Claims (15)
    [1]
    1. Optical sensor (100, 400) for measuring at least one dissolved gas in a measuring medium comprisinga sensor head (102);a shaft element (106, 206, 406) with a recess (110) for a sensitive element (108, 408); anda cylindrical sensor shaft (104), which is arranged between the sensor head (102) and the shaft element (106, 206, 406);characterized in that the shaft element (106, 206, 406) comprises a hydrophilic outer surface (118, 218).
    [2]
    2. Optical sensor according to claim 1, characterized in that the shaft element (106, 206) comprises a beveled end surface (116) in which the recess (110) for the sensitive element (108) is arranged, and that the hydrophilic outer surface ( 218) of the shaft element (206) comprises at least the beveled end surface (116).
    [3]
    3. Optical sensor according to claim 2, characterized in that the bevelled end surface (116) of the shaft element (106, 206) has an angle between 25 and 45 degrees and preferably of approximately 30 degrees.
    [4]
    4. Optical sensor according to one of claims 1 to 3, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206, 406) has a surface roughness of Ra ≤ 1 µm and in particular of Ra ≤ 0.4 µm .
    [5]
    5. Optical sensor according to one of claims 1 to 4, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206, 406) has a contact angle θ ≤ 60 °, preferably between 0 ≥ 40 ° and θ ≤ 55 ° and in particular between θ ≥ 45 ° and θ ≤ 50 °.
    [6]
    6. Optical sensor according to one of claims 1 to 4, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206, 406) has a contact angle θ ≤ 60 °, preferably between θ ≥ 10 ° and θ ≤ 20 ° and in particular between θ ≥ 12 ° and θ ≤ 17 °.
    [7]
    7. Optical sensor according to one of claims 1 to 6, characterized in that the shaft element (106, 206, 406) consists of a metal, preferably stainless steel.
    [8]
    8. Optical sensor according to one of claims 1 to 7, characterized in that it further comprises a sensitive element (108, 408) which is arranged in a recess (110) in the shaft element (106, 206, 406) and in the operation of the optical sensor is in contact with the measuring medium (416).
    [9]
    9. Optical sensor according to one of claims 1 to 8, characterized in that it further comprises a measuring arrangement which comprises optical and electronic components for measuring the at least one dissolved gas and is arranged in the sensor head (102) and in the sensor shaft (104).
    [10]
    10. A method for producing an optical sensor (100) for measuring at least one dissolved gas in a measuring medium according to one of the preceding claims, wherein the optical sensor (100, 400)a sensor head (102);a shaft element (106, 206, 406) with a recess (116) for a sensitive element (108, 408); anda cylindrical sensor shaft (104) which is arranged between the sensor head (102) and the shaft element (106, 206, 406);the method comprising the following steps:Producing a shaft element (106, 206, 406) with a recess (110) for a sensitive element (108, 408); andGenerating a hydrophilic outer surface (118, 218) on the shaft element (106).
    [11]
    11. The method according to claim 10, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206) is generated by sandblasting, chemical etching and / or grinding.
    [12]
    12. The method according to any one of claims 10 or 11, characterized in that the manufacture of the shaft element (106, 206) further comprises the configuration of a bevelled end surface (116) with an angle between 25 and 45 degrees and preferably of approximately 30 degrees.
    [13]
    13. The method according to any one of claims 10 to 12, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206), which comprises at least the beveled end surface (116), with a surface roughness of Ra ≤ 1 µm and in particular of Ra ≤ 0.4 µm is generated.
    [14]
    14. The method according to any one of claims 10 to 13, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206, 406) with a contact angle θ ≤ 60 °, preferably between θ ≥ 40 ° and θ ≤ 55 ° and in particular between θ ≥ 45 ° and θ ≤ 50 °.
    [15]
    15. The method according to any one of claims 10 to 13, characterized in that the hydrophilic outer surface (118, 218) of the shaft element (106, 206, 406) with a contact angle θ ≤ 60 °, preferably between θ ≥ 10 ° and θ ≤ 20 ° and in particular between θ ≥ 12 ° and θ ≤ 17 °.
    类似技术:
    公开号 | 公开日 | 专利标题
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    同族专利:
    公开号 | 公开日
    EP3176566A1|2017-06-07|
    CH711881A2|2017-06-15|
    CN206627428U|2017-11-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    DE102013103735A1|2013-04-15|2014-10-16|Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG|Arrangement for the optical measurement of one or more physical, chemical and / or biological process variables of a medium|
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    法律状态:
    2019-11-29| AZW| Rejection (application)|
    优先权:
    申请号 | 申请日 | 专利标题
    EP15197723.8A|EP3176566A1|2015-12-03|2015-12-03|Optical sensor for measuring dissolved gases|
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