JPH08119684A - Joining between porous glass and vitreous supporting base - Google Patents
Joining between porous glass and vitreous supporting baseInfo
- Publication number
- JPH08119684A JPH08119684A JP5200427A JP20042793A JPH08119684A JP H08119684 A JPH08119684 A JP H08119684A JP 5200427 A JP5200427 A JP 5200427A JP 20042793 A JP20042793 A JP 20042793A JP H08119684 A JPH08119684 A JP H08119684A
- Authority
- JP
- Japan
- Prior art keywords
- porous glass
- joining
- bonding
- glass
- vitreous
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Joining Of Glass To Other Materials (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多孔質ガラスの細孔を
感応体とする、ガスセンサー、液体イオンセンサー等の
各種機能センサー素子の製造方法に関し、特に多孔質ガ
ラスの接合方法に係わるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing various functional sensor elements such as gas sensors and liquid ion sensors, which use pores of porous glass as a sensitizer, and particularly to a method for joining porous glass. Is.
【０００２】[0002]
【従来技術】多孔質ガラスは、その細孔に表面処理ある
いは特定物質を担持させることによって、各種のガス分
離体、液体分離体、電解質分離体、あるいは触媒担体、
酵素固定用担体等に利用され始めている。更に、多孔質
ガラスの細孔を感応体とする各種の機能センサーの開発
も注目されている。2. Description of the Related Art Porous glass has various kinds of gas separators, liquid separators, electrolyte separators, or catalyst carriers, which are surface-treated or have specific substances supported on their pores.
It is beginning to be used as a carrier for immobilizing enzymes. Furthermore, the development of various functional sensors that use the pores of porous glass as a sensitizer has attracted attention.
【０００３】前記する様な多孔質ガラスの各種の応用例
として、例えば特開昭６１−１７０６４５にはイオン感
応物質を細孔に固定した多孔質ガラスを感応膜とするイ
オン選択性電極がある。ここでは多孔質ガラスをガラス
管の先端に固定するのにパラフィルムを用いている。こ
の例に限らず各種の機能センサーの感応素子の感応体と
して多孔質ガラスを使用する場合、多孔質ガラスをガラ
ス管等の支持基台に接合固定するには、有機接着剤を用
いたり、あるいは樹脂性のリング状部材で接合部をバン
ド締めした上に、金属又は樹脂製のキャップを被覆する
ものであった。As various applications of the above-mentioned porous glass, for example, Japanese Patent Laid-Open No. 61-170645 discloses an ion selective electrode using a porous glass having an ion sensitive substance fixed in its pores as a sensitive membrane. Here, parafilm is used to fix the porous glass to the tip of the glass tube. Not limited to this example, when using porous glass as the sensitive body of the sensitive element of various functional sensors, an organic adhesive is used to bond and fix the porous glass to a supporting base such as a glass tube, or The joint part is band-tightened with a resinous ring-shaped member, and then a metal or resin cap is covered.
【０００４】しかしながら、上記の様な樹脂による固定
や、有機接着剤による接合では、高温環境や温度差の激
しい環境下に長時間さらされたり環境中の液体や雰囲気
によっては、樹脂や有機接着剤が劣化し、これによって
感応素子の剥離が起ったり、センサーとしての感度特性
値が不安定となり易くなるので、感応素子の使用環境は
著しく制限されている。However, in fixing with a resin or joining with an organic adhesive as described above, the resin or the organic adhesive may be exposed to a high temperature environment or an environment with a large temperature difference for a long time, or depending on the liquid or atmosphere in the environment. Deteriorates, and this tends to cause peeling of the sensitive element and instability of the sensitivity characteristic value of the sensor, so that the operating environment of the sensitive element is significantly limited.
【０００５】また、このような使用環境から接合部を保
護するために設けた金属又は樹脂製のキャップは、図３
に示すように、多孔質ガラスの一部をも被覆することに
なるので、感応部の面積が減少し感度特性値を低下させ
ることになる。更に、素子全体の小型、軽量化の妨げと
なる。Further, the cap made of metal or resin provided to protect the joint portion from such a use environment is shown in FIG.
As shown in (1), since the porous glass is also partially covered, the area of the sensitive portion is reduced and the sensitivity characteristic value is reduced. Further, this hinders reduction in size and weight of the entire device.
【０００６】一方、樹脂による固定や、有機接着剤によ
る接合よりも耐環境性に比較的優れる接合方法として、
低融点ガラスによるガラス接合が考えられるが、接合時
に６００℃以上の加熱が必要となるので多孔質ガラスが
変質し、孔がふさがるので実質的に適用出来ない。On the other hand, as a joining method which is relatively superior in environmental resistance as compared with fixing with a resin or joining with an organic adhesive,
Glass bonding with a low-melting glass is conceivable, but heating at 600 ° C. or higher is required at the time of bonding, so that the porous glass is deteriorated and the pores are closed, so that it is practically not applicable.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、多孔質ガラ
スの細孔を感応体とする各種の機能センサーの開発にお
いて障害となっていた、多孔質ガラスとガラス質支持基
台との接合に関して、より耐環境性に優れる接合が可能
な多孔質ガラスの接合方法を提供することにある。DISCLOSURE OF THE INVENTION The present invention relates to the joining of the porous glass and the vitreous support base, which has been an obstacle in the development of various functional sensors using the pores of the porous glass as a sensitive body. Another object of the present invention is to provide a method for joining porous glass capable of joining with more excellent environmental resistance.
【０００８】[0008]
【課題を解決するための手段】上記した課題を解決する
ための第１の本発明は次の各工程からなる接合方法によ
って解決される。 （イ）多孔質ガラスと、結合部材とを陽極接合する第１
工程 （ロ）前記第１工程によって得られる接合体の結合部材
面と、ガラス質支持基台とを陽極接合する第２工程（た
だし、結合部材はケイ素系無機物質であって、Si、Si
C、Si3N4から選択される１種）The first aspect of the present invention for solving the above-mentioned problems is solved by a joining method comprising the following steps. (A) First anodic bonding of the porous glass and the bonding member
Step (b) A second step of anodic-bonding the bonding member surface of the bonded body obtained by the first step and the vitreous support base (provided that the bonding member is a silicon-based inorganic substance, Si, Si
One selected from C and Si 3 N 4 )
【０００９】また、第２の本発明は次の各工程からなる
ものである。 （イ）ガラス質支持基台と、結合部材とを陽極接合する
第１工程 （ロ）前記第１工程によって得られる接合体の結合部材
面と、多孔質ガラスとを陽極接合する第２工程（ただ
し、結合部材はケイ素系無機物質であって、Si、SiC、S
i3N4から選択される１種）The second aspect of the present invention comprises the following steps. (A) First step of anodic bonding the vitreous support base and the bonding member (b) Second step of anodic bonding the bonding member surface of the bonded body obtained in the first step and the porous glass However, the bonding member is a silicon-based inorganic material, and is composed of Si, SiC, S
one selected from i 3 N 4 )
【００１０】[0010]
【作用】本発明で用いる陽極接合は、接合部材間に高温
雰囲気下で直流高電圧を印加させて、接合界面に高電界
を生じさせることによって、接着剤を介すること無く均
一で強固な接合ができるものである。In the anodic bonding used in the present invention, a high DC voltage is applied between the bonding members in a high temperature atmosphere to generate a high electric field at the bonding interface, so that a uniform and strong bonding can be achieved without an adhesive. It is possible.
【００１１】結合部材は、陽極接合によって、多孔質ガ
ラスとガラス質支持基台とを接合固定する為の必須の部
材である。一般に多孔質ガラスとガラス質支持基台のよ
うにガラス−ガラスの陽極接合では、接合界面に陽極接
合に必要な高電界が生じないので接合できないが、ケイ
素系無機物質を結合部材として用いれば、多孔質ガラス
と結合部材、並びに結合部材とガラス質支持基台の接合
界面には陽極接合に必要な高電界が生じて陽極接合が可
能となり、多孔質ガラスとガラス質支持基台は結合部材
を介して、一体に接合固定できるようになる。The joining member is an essential member for joining and fixing the porous glass and the vitreous support base by anodic bonding. Generally, in the anodic bonding of glass-glass like a porous glass and a glassy support base, it cannot be bonded because a high electric field required for anodic bonding does not occur at the bonding interface, but if a silicon-based inorganic substance is used as a bonding member, A high electric field required for anodic bonding is generated at the bonding interface between the porous glass and the bonding member, and the bonding member and the vitreous support base, and anodic bonding becomes possible. Through this, it becomes possible to integrally bond and fix.
【００１２】使用できる結合部材は、ケイ素系無機物質
であって、シリコン（Si）、炭化ケイ素（SiC）、窒化
ケイ素（Si3N4）の何れかが使用できる。The bonding member that can be used is a silicon-based inorganic material, and any of silicon (Si), silicon carbide (SiC), and silicon nitride (Si 3 N 4 ) can be used.
【００１３】多孔質ガラスは一般的にシリカ含有率が高
くなっているが、ガラス組成中に微量にＮａ＋、あるい
はＬｉ＋等のアルカリイオンを含有している必要があ
る。また、多孔質ガラス内部の細孔表面には、必要とす
るセンサー機能を発揮させる物質を予め担持させておい
ても良い。なお、陽極接合の際に４００℃程度の高温環
境に保持されるが、この程度の温度では多孔質ガラスは
変質しない。Porous glass generally has a high silica content, but it is necessary for the glass composition to contain a small amount of alkali ions such as Na + or Li + . In addition, the surface of the pores inside the porous glass may be previously loaded with a substance that exerts the required sensor function. It should be noted that the anodic bonding is maintained in a high temperature environment of about 400 ° C., but at this temperature, the porous glass does not deteriorate.
【００１４】ガラス質支持基台はパイレックスガラス等
の低膨張のホウケイ酸ガラスや、結晶化ガラスが使用で
きる。また、多孔質ガラス同様に組成中に微量のＮ
ａ＋、あるいはＬｉ＋等のアルカリイオンを含有してい
る必要がある。For the vitreous support base, low expansion borosilicate glass such as Pyrex glass or crystallized glass can be used. In addition, like the porous glass, a small amount of N in the composition
It is necessary to contain alkali ions such as a + or Li + .
【００１５】本発明によって接合される界面は、上記し
た何れの発明においても、多孔質ガラスと結合部材、並
びに結合部材とガラス質支持基台の各両面であるが、互
いに接合される被接合面は平滑であるほうが好ましい。In any of the above-mentioned inventions, the interfaces to be joined according to the present invention are both surfaces of the porous glass and the joining member, and the joining member and the vitreous support base. Is preferably smooth.
【００１６】多孔質ガラス、結合部材、及びガラス質支
持基台の各部材の熱膨張係数（以後αと称する）が近似
する場合は接合固定後の応力歪みは小さくなる。応力歪
みが十分小さければ、接合部の剥離や変形は発生しな
い。一例として、αが３０（×１０-7／℃）程度で孔径
０．５〜２μｍを有する多孔質ガラスに対しては、結合
部材としてαが３０（×１０-7／℃）程度のSi、ガラス
質支持基台としてαが３２（×１０-7／℃）程度のパイ
レックスガラスの組合わせができる。また、結合部材は
多孔質ガラスとガラス質支持基台の両部材に挟まれるこ
とになるので、多孔質ガラスと結合部材、又は結合部材
とガラス質支持基台の熱膨張係数に幾らか差異が生じて
も、結合部材の厚みを調整することによって、応力歪み
による接合部の剥離や変形は防止できる。When the thermal expansion coefficient (hereinafter referred to as α) of each member of the porous glass, the bonding member, and the vitreous support base is close to each other, the stress strain after bonding and fixing becomes small. If the stress strain is sufficiently small, peeling or deformation of the joint does not occur. As an example, alpha is 30 (× 10 -7 / ℃) for the porous glass with a pore size 0.5~2μm extent, alpha as coupling member 30 (× 10 -7 / ℃) about Si, As the vitreous support base, a combination of Pyrex glass having α of about 32 (× 10 −7 / ° C.) can be used. Further, since the bonding member is sandwiched between both members of the porous glass and the vitreous support base, there is some difference in the coefficient of thermal expansion between the porous glass and the bonding member, or between the binding member and the vitreous support base. Even if it occurs, by adjusting the thickness of the coupling member, peeling or deformation of the joint portion due to stress strain can be prevented.
【００１７】[0017]
【実施例】以下に本発明を図示の実施例によって更に詳
細に説明する。 （実施例１）第１の発明に基づく接合方法を図１に示
す。多孔質ガラス１は、直径５mmφ、厚み２mmの円柱状
に加工されたものであり、ジルコニア含有の高ケイ酸ガ
ラスであって数％程度のNa2Oを含有し、孔径分布が約
０．５〜２μｍで平均熱膨張係数が約３０（×１０-7／
℃）程度を呈するものである。結合部材２は外径５mm
φ、肉厚１mm、厚み０．３mmのリング状に加工されたSi
を用いた。支持基台３は外径５mmφ、肉厚１mm、厚み１
０mmのパイプ状のパイレックスガラスを用いた。なお、
いずれの部材の被接合面も平滑となるように加工を施し
ているものを使用する。The present invention will be described below in more detail with reference to the illustrated embodiments. (Embodiment 1) A joining method based on the first invention is shown in FIG. The porous glass 1 is processed into a cylindrical shape having a diameter of 5 mmφ and a thickness of 2 mm, is a high silicate glass containing zirconia, contains about 2 % of Na 2 O, and has a pore size distribution of about 0.5. The average thermal expansion coefficient is about 30 (× 10 -7 /
C.) is exhibited. Connecting member 2 has an outer diameter of 5 mm
φ processed into a ring shape with a wall thickness of 1 mm and a thickness of 0.3 mm
Was used. The support base 3 has an outer diameter of 5 mmφ, a wall thickness of 1 mm, and a thickness of 1
A 0 mm pipe-shaped Pyrex glass was used. In addition,
All the members to be joined are processed so that the surfaces to be joined are smooth.
【００１８】接合に於ける第１の工程は、多孔質ガラス
１と結合部材２（Si）とを陽極接合するものであるが、
接合に際しては、電熱ヒーター等によって３５０℃に加
熱保持しながら、多孔質ガラス１を陰極、結合部材２
（Si）を陽極となるように接触させて直流電圧を印加す
る。例えばＤＣ４００Ｖ、印加時間２分で陽極接合が完
了する。続く第２の工程は、第１の工程で接合された接
合体１０の結合部材（Si）面を陽極、支持基台３（パイ
レックスガラス）を陰極となるように接触させて直流電
圧を印加するものである。その際も第１工程と同様な接
合条件で陽極接合が完了する。The first step in bonding is to anodic bond the porous glass 1 and the bonding member 2 (Si).
Upon joining, the porous glass 1 is used as the cathode and the joining member 2 while being heated and held at 350 ° C. by an electric heater or the like.
A direct current voltage is applied by contacting (Si) so as to serve as an anode. For example, the anodic bonding is completed at 400V DC for 2 minutes. In the subsequent second step, the joining member (Si) surface of the joined body 10 joined in the first step is brought into contact with the anode and the support base 3 (Pyrex glass) is brought into contact with the cathode to apply a DC voltage. It is a thing. Also in that case, the anodic bonding is completed under the same bonding conditions as in the first step.
【００１９】この様にして得られた多孔質ガラス−Si−
パイレックスガラスの一体接合物の引張強度を測定した
が、多孔質ガラスの母材破壊が起こるほどに十分な接合
強度を有していた。Porous glass-Si-obtained in this way
The tensile strength of the Pyrex glass unitary joint was measured, and it was found that the joint strength was sufficient so that the base material of the porous glass was broken.
【００２０】（実施例２）第２の発明に基づく接合方法
を図２に示す。結合部材として実施例１と同一形状で材
質としてSiCを用い、多孔質ガラスと支持基台（パイレ
ックスガラス）は同一形状で同一材質のものを用いる。
接合に於ける第１の工程は、結合部材２ａ（SiC）と支
持基台３（パイレックスガラス）とを陽極接合するもの
であるが、接合に際しては、電熱ヒーター等によって３
５０℃に加熱保持しながら、結合部材２ａ（SiC）を陽
極、支持基台３（パイレックスガラス）を陰極となるよ
うに接触させて、例えば実施例１と同一条件で直流電圧
を印加することによって陽極接合が完了する。続く第２
の工程は、第１の工程で接合された接合体１０ａの結合
部材（SiC）面を陽極、多孔質ガラス１の端面を陰極と
なるように接触させて直流電圧を印加するものである。
その際も例えば第１工程と同様な接合条件で陽極接合が
完了する。(Embodiment 2) A joining method based on the second invention is shown in FIG. SiC is used as the connecting member in the same shape as in Example 1, and the porous glass and the support base (Pyrex glass) are the same in shape and the same material.
The first step in bonding is to anodic bond the bonding member 2a (SiC) and the support base 3 (Pyrex glass).
While heating and holding at 50 ° C., the bonding member 2a (SiC) is brought into contact with the anode and the support base 3 (Pyrex glass) is brought into contact with the cathode, and a DC voltage is applied under the same conditions as in Example 1, for example. Anodic bonding is completed. The second that follows
In this step, the bonding member (SiC) surface of the bonded body 10a bonded in the first step is brought into contact with the anode and the end surface of the porous glass 1 is brought into contact with the cathode to apply a DC voltage.
Also in that case, for example, the anodic bonding is completed under the same bonding conditions as in the first step.
【００２１】[0021]
【発明の効果】本発明の多孔質ガラスとガラス質支持基
台の接合方法によれば、接合固定の際に樹脂や有機接着
剤が不要となるので、耐環境性に優れる接合が可能とな
る。よって、本発明の接合方法によって得られる多孔質
ガラスの感応素子は、接合面が環境中の温度、雰囲気、
液体等によって劣化しにくいので、接合面の剥離が起こ
りにくく、センサーとしての感度特性が安定する。ま
た、金属や樹脂製のキャプも不要となるので、感応部
（多孔質ガラスの細孔）の面積が従来よりも広くなり感
度特性が向上する。更に、素子全体の小型、軽量化が容
易となる。このことから、本発明の接合方法は産業の発
展に寄与するものは多大であると確信する次第である。EFFECTS OF THE INVENTION According to the method of joining the porous glass and the vitreous support base of the present invention, a resin and an organic adhesive are not required at the time of joining and fixing, so that the joining with excellent environmental resistance is possible. . Therefore, the sensitive element of the porous glass obtained by the bonding method of the present invention, the bonding surface is the temperature of the environment, the atmosphere,
Since it is less likely to be deteriorated by a liquid or the like, peeling of the joint surface is less likely to occur, and the sensitivity characteristic of the sensor is stable. Further, since the cap made of metal or resin is not required, the area of the sensitive portion (the pores of the porous glass) is wider than in the conventional case, and the sensitivity characteristic is improved. Further, it becomes easy to reduce the size and weight of the entire device. From this, it is believed that the joining method of the present invention greatly contributes to industrial development.
【図１】本発明の接合方法を示す説明図である。FIG. 1 is an explanatory view showing a joining method of the present invention.
【図２】本発明の別の接合方法を示す説明図である。FIG. 2 is an explanatory view showing another joining method of the present invention.
【図３】従来の接合方法によって製造された感応素子の
一部縦断面図である。FIG. 3 is a partial vertical sectional view of a sensitive element manufactured by a conventional bonding method.
１ 多孔質ガラス ２、２ａ 結合部材 ３ 支持基台 1 Porous glass 2, 2a Bonding member 3 Support base
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【手続補正書】[Procedure amendment]
【提出日】平成６年６月８日[Submission date] June 8, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】追加[Correction method] Added
【補正内容】[Correction content]
【図１】 FIG.
【図２】 [Fig. 2]
【図３】 [Figure 3]
Claims (2)
センサー素子の製造において、次の各工程からなる、多
孔質ガラスとガラス質支持基台の接合方法 （イ）多孔質ガラスと、結合部材とを陽極接合する第１
工程 （ロ）前記第１工程によって得られる接合体の結合部材
面と、ガラス質支持基台とを陽極接合する第２工程（た
だし、結合部材はケイ素系無機物質であって、Si、Si
C、Si3N4から選択される１種）1. A method for joining a porous glass and a vitreous support base, which comprises the following steps in the production of a functional sensor element having pores of the porous glass as a sensitive body: (a) porous glass; First anodic bonding with a coupling member
Step (b) A second step of anodic-bonding the bonding member surface of the bonded body obtained by the first step and the vitreous support base (provided that the bonding member is a silicon-based inorganic substance, Si, Si
One selected from C and Si 3 N 4 )
センサー素子の製造において、次の各工程からなる、多
孔質ガラスと支持基台の接合方法 （イ）ガラス質支持基台と、結合部材とを陽極接合する
第１工程 （ロ）前記第１工程によって得られる接合体の結合部材
面と、多孔質ガラスとを陽極接合する第２工程（ただ
し、結合部材はケイ素系無機物質であって、Si、SiC、S
i3N4から選択される１種）2. A method for joining a porous glass and a support base, which comprises the following steps in the production of a functional sensor element having pores of the porous glass as a sensitive body: (a) a glass support base; First step of anodic bonding the bonding member (b) Second step of anodic bonding the bonding member surface of the bonded body obtained by the first step and the porous glass (provided that the bonding member is a silicon-based inorganic substance) Yes, Si, SiC, S
one selected from i 3 N 4 )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5200427A JPH08119684A (en) | 1993-07-20 | 1993-07-20 | Joining between porous glass and vitreous supporting base |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5200427A JPH08119684A (en) | 1993-07-20 | 1993-07-20 | Joining between porous glass and vitreous supporting base |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08119684A true JPH08119684A (en) | 1996-05-14 |
Family
ID=16424123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5200427A Pending JPH08119684A (en) | 1993-07-20 | 1993-07-20 | Joining between porous glass and vitreous supporting base |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08119684A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3517944A1 (en) * | 2018-01-30 | 2019-07-31 | Mettler-Toledo GmbH | Measurement unit for an ion-sensitive solid-state electrode and ion-sensitive electrode |
| EP3517943A1 (en) * | 2018-01-30 | 2019-07-31 | Mettler-Toledo GmbH | Ion-sensitive glass electrode, measurement unit and method for manufacturing |
-
1993
- 1993-07-20 JP JP5200427A patent/JPH08119684A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3517944A1 (en) * | 2018-01-30 | 2019-07-31 | Mettler-Toledo GmbH | Measurement unit for an ion-sensitive solid-state electrode and ion-sensitive electrode |
| EP3517943A1 (en) * | 2018-01-30 | 2019-07-31 | Mettler-Toledo GmbH | Ion-sensitive glass electrode, measurement unit and method for manufacturing |
| WO2019149704A1 (en) * | 2018-01-30 | 2019-08-08 | Mettler-Toledo Gmbh | Ion-sensitive electrode, measurement unit and method for manufacturing |
| WO2019149705A1 (en) * | 2018-01-30 | 2019-08-08 | Mettler-Toledo Gmbh | Measurement unit for an ion-sensitive solid-state electrode and ion-sensitive electrode |
| CN111837030A (en) * | 2018-01-30 | 2020-10-27 | 梅特勒-托莱多有限公司 | Ion-sensitive electrode, measuring cell and method of manufacture |
| JP2021511517A (en) * | 2018-01-30 | 2021-05-06 | メトラー−トレド ゲーエムベーハー | Measurement unit for ion-sensitive solid electrodes and ion-sensitive electrodes |
| US11726055B2 (en) | 2018-01-30 | 2023-08-15 | Mettler-Toledo Gmbh | Measurement unit for an ion-sensitive solid-state electrode and ion-sensitive electrode |
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