JP2005207887A - Electrode support member and electrochemical sensor - Google Patents

Electrode support member and electrochemical sensor Download PDF

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JP2005207887A
JP2005207887A JP2004014810A JP2004014810A JP2005207887A JP 2005207887 A JP2005207887 A JP 2005207887A JP 2004014810 A JP2004014810 A JP 2004014810A JP 2004014810 A JP2004014810 A JP 2004014810A JP 2005207887 A JP2005207887 A JP 2005207887A
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electrode
electrochemical sensor
support member
glass
electrode support
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Masaharu Yamasato
昌春 山里
Taisuke Nakano
泰介 中野
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DKK TOA Corp
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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode support member of an electrochemical sensor, formed of a glass composition which is improved in weldability with a sensing part, such as a glass-sensing film, a platinum electrode or the like or a junction made of porous ceramics, having relatively low-temperature softening properties and proper processability, fine processability, resistance to water, weatherability and transparency, and provide also an electrochemical sensor. <P>SOLUTION: The electrode support member of the electrochemical sensor is formed of a glass composition, containing 60-75% SiO<SB>2</SB>, 2-14% Na<SB>2</SB>O, 0-9% Li<SB>2</SB>O, 1-9% K<SB>2</SB>O (where Na<SB>2</SB>O+Li<SB>2</SB>O+K<SB>2</SB>O: 10-25%), 0-9% SrO, 1-9% CaO, 1-6% BaO, 0-6% MgO, 0-6% ZnO (where SrO+CaO+BaO+MgO+ZnO:10-25%) and 0-6% Al<SB>2</SB>O<SB>3</SB>on weight percent basis. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、ｐＨ電極、電気伝導率セル、ＯＲＰ（酸化還元電位差）電極、ポーラログラフ式電極、ガルバニ式電極などの電気化学式センサの電極支持部材及び電気化学式センサに関するものである。   The present invention relates to an electrode support member for an electrochemical sensor such as a pH electrode, an electrical conductivity cell, an ORP (oxidation-reduction potential difference) electrode, a polarographic electrode, a galvanic electrode, and an electrochemical sensor.

従来、例えば、ｐＨ電極では、感応部としてのガラス感応膜（ｐＨ感応膜）は、通常、ガラスで形成された電極支持部材の先端に熔着により取り付けられる。ガラス感応膜の材料としては、例えばＳｉＯ2、ＢａＯ、Ｌｉ2Ｏ、Ｌａ2Ｏ3、Ｃｓ2ＣＯ3、ＴｉＯ2などを含有する（更に、Ｔａ2Ｏ5、Ｐｒ2Ｏ3、Ｃｒ2Ｏ3などを含有していることがある。）、Ｌｉ系ガラスが用いられる。そして、多くの有用なＬｉ系ガラスの熱膨張係数（線膨張係数：以下、同様。）は、８〜１０．５×１０-6／℃である。 Conventionally, for example, in a pH electrode, a glass sensitive film (pH sensitive film) as a sensitive part is usually attached to the tip of an electrode support member made of glass by welding. Examples of the material for the glass sensitive film include SiO 2 , BaO, Li 2 O, La 2 O 3 , Cs 2 CO 3 , TiO 2 and the like (further, Ta 2 O 5 , Pr 2 O 3 , Cr 2 O). 3 or the like), Li-based glass is used. The thermal expansion coefficient (linear expansion coefficient: the same applies hereinafter) of many useful Li-based glasses is 8 to 10.5 × 10 −6 / ° C.

又、電気化学式センサとして、例えば、電気伝導率セル、ＯＲＰ（酸化還元電位差）電極、ポーラログラフ式電極或いはガルバニ式電極などにおいては、感応部（作用極或いは対極）たる金属極として白金が多く用いられ、ガラスで形成された電極支持部材の先端から露出するように封着される。そして、白金の膨張係数は８．９×１０-6／℃である。 Further, as an electrochemical sensor, for example, platinum is often used as a metal electrode as a sensitive part (working electrode or counter electrode) in an electric conductivity cell, an ORP (oxidation-reduction potential difference) electrode, a polarographic electrode, or a galvanic electrode. The electrode supporting member made of glass is sealed so as to be exposed from the tip. The expansion coefficient of platinum is 8.9 × 10 −6 / ° C.

更に、ｐＨ電極、ＯＲＰ電極などと共に用いられるか或いは複合電極として一体的に形成される比較電極においては、試料液との電気的導通をとるために、ジャンクション（液絡部）が設けられる。このようなジャンクションを設けるなどのために、ガラスで形成された電極支持部材に多孔質セラミックスが封入されることがある。そしてこの多孔質セラミックスの熱膨張係数は、８〜１０．５×１０-6／℃である。 Further, in the comparison electrode that is used together with the pH electrode, the ORP electrode, or the like or is integrally formed as a composite electrode, a junction (liquid junction) is provided in order to establish electrical continuity with the sample solution. In order to provide such a junction, porous ceramics may be enclosed in an electrode support member made of glass. The thermal expansion coefficient of the porous ceramic is 8 to 10.5 × 10 −6 / ° C.

上記ガラス感応膜、白金電極などの感応部、又は、多孔質セラミックスと電極支持部材との熔着、封着或いは封入（ここでは、総じて「熔着」という。）を良好に行い、又この熔着部分における温度変化によるクラック防止などのためには、電極支持部材と、上記感応部又は多孔質セラミックスとの熱膨張係数を近くすることが必要である。   The above-described glass sensitive film, sensitive part such as platinum electrode, or porous ceramic and electrode support member are well welded, sealed or sealed (herein, generally referred to as “welding”). In order to prevent cracks due to temperature changes at the wearing portion, it is necessary to make the thermal expansion coefficients of the electrode support member and the sensitive part or porous ceramics close to each other.

又、電気化学式センサの電極支持部材としては、製造の容易性（加工性、細工性）、耐水性、耐候性が良く、又透明性が良いことも重要となる。   In addition, as an electrode support member for an electrochemical sensor, it is also important that manufacturing ease (workability, workability), water resistance, weather resistance, and transparency are good.

斯かる要求に応える電極支持部材用の材料として、従来、一般にＰｂＯを含有するガラス組成物（以下「鉛ガラス」という。）が多用されている。斯かるガラス組成物は、一例として、ＳｉＯ2、ＰｂＯの他に、ＢａＯ、Ａｌ2Ｏ3、Ｎａ2Ｏ、Ｋ2Ｏなどを含有する。 As a material for an electrode support member that meets such requirements, a glass composition containing PbO (hereinafter referred to as “lead glass”) has been generally used. As an example, such a glass composition contains BaO, Al 2 O 3 , Na 2 O, K 2 O and the like in addition to SiO 2 and PbO.

斯かる鉛ガラスは、熱膨張係数が９．５×１０-6／℃と、上記ガラス感応膜、白金電極などの感応部、又は、多孔質セラミックスのそれと近く、熔着性が良い。しかも、鉛ガラスは、低温軟化性で加工性、細工性が良く、しかも透明性、耐水性、耐候性も良い。 Such a lead glass has a thermal expansion coefficient of 9.5 × 10 −6 / ° C., close to that of the above-mentioned glass sensitive film, a sensitive part such as a platinum electrode, or porous ceramics, and has good weldability. Moreover, lead glass is soft at low temperature, has good workability and workability, and has good transparency, water resistance and weather resistance.

しかしながら、鉛ガラスは、鉛を使用していることで、製品を廃棄する場合、環境汚染をしないように廃棄する必要があり、廃棄コストが高くなる。このような、環境配慮の観点から、鉛を含有しないガラス組成が望まれるようになってきている。   However, since lead glass uses lead, when the product is discarded, it is necessary to discard the product so as not to pollute the environment, and the disposal cost increases. In view of such environmental considerations, a glass composition containing no lead has been desired.

又、鉛ガラスは、上述のように低温軟化性で加工性、細工性が良いが、例えば、ｐＨ電極などの製造工程にて、鉛ガラスの切り口を炙って焼きなますとき、炙り過ぎると鉛が分離して切り口が鉛色になるなど、ガラス加工に熟練を要するものであった。   In addition, lead glass is soft at low temperatures and has good workability and workability as described above. For example, in the manufacturing process of pH electrodes, lead glass is cut and annealed. However, it was necessary to have skill in glass processing.

ところで、特許文献１には、鉛を含有しないモールドプレス成形レンズ用のガラス組成物として、ＳｉＯ2−Ｂ2Ｏ3−Ｎｂ2Ｏ5−（Ｔａ2Ｏ5）−ＴｉＯ2−（ＺｒＯ2）−Ｌａ2Ｏ3−Ａｌ2Ｏ3−ＺｎＯ−（ＣａＯ）−（ＳｒＯ）−（Ｌｉ2Ｏ）−（Ｎａ2Ｏ）−（Ｋ2Ｏ）（カッコ内の成分はいずれも０％を含む。）系が開示されている。又、特許文献２には、鉛を含有しない絶縁用ガラス組成物として、ＺｎＯ−Ｂｉ2Ｏ3−Ｂ2Ｏ3−ＳｉＯ2−ＲＯ（Ｒは二価金属元素）系のガラス組成が開示されている。Ｂ2Ｏ3を含むガラスは、ガラス鍋などとしても使用される。しかしながら、これらのガラス組成は、ガラス感応膜、白金電極などの感応部、又は、多孔質セラミックスなどと熱膨張係数が適合しないか、加工温度が高く、電気化学式センサの電極支持部材用の材料としては向いていない。 By the way, Patent Document 1 discloses SiO 2 —B 2 O 3 —Nb 2 O 5 — (Ta 2 O 5 ) —TiO 2 — (ZrO 2 ) as a glass composition for a mold press-molded lens not containing lead. -La 2 O 3 -Al 2 O 3 -ZnO- (CaO) - (SrO) - (Li 2 O) - (Na 2 O) - (K 2 O) ( component in brackets including 0% none .) System is disclosed. Patent Document 2 discloses a ZnO—Bi 2 O 3 —B 2 O 3 —SiO 2 —RO (R is a divalent metal element) -based glass composition as an insulating glass composition containing no lead. ing. Glass containing B 2 O 3 is also used as a glass pan or the like. However, these glass compositions are incompatible with glass sensitive films, sensitive parts such as platinum electrodes, or porous ceramics, etc., or have a high processing temperature, and are used as materials for electrode support members of electrochemical sensors. Is not suitable.

又、例えば瓶の作製などに使用される一般的なソーダ石灰ガラスは、熱膨張係数がガラス感応膜、白金電極、又は、多孔質セラミックスと近いが、寿命が短く、アルカリに弱く、耐水性、耐候性が悪く、又電極支持管の端部に感応膜を熔着する際に、電極支持管のガラス組成が感応膜のガラス組成に混ざると感応膜の特性が悪くなることがあり、電気化学式センサの電極支持部材としては好ましくない。   In addition, for example, a general soda lime glass used for producing a bottle has a thermal expansion coefficient close to that of a glass-sensitive film, a platinum electrode, or porous ceramics, but has a short life, weak to alkali, water resistance, The weather resistance is poor, and when the sensitive film is welded to the end of the electrode support tube, the characteristics of the sensitive film may deteriorate if the glass composition of the electrode support tube is mixed with the glass composition of the sensitive film. It is not preferable as an electrode support member of the sensor.

斯かる従来の技術背景に鑑み、本発明者らは、ガラス感応膜、白金電極などの感応部、又は、多孔質セラミックスとの熔着性が良く、比較的低温軟化性で加工性、細工性が良く、しかも耐水性、耐候性、透明性も良好であり、電気化学式センサの電極支持部材として有用なガラス組成を探査したが、斯かる要求に合致する適当なガラス組成は見当たらない。
特許第３４２３６７３号公報 特許第３４２４７００号公報 In view of such a conventional technical background, the present inventors have good weldability with a sensitive part such as a glass sensitive film, a platinum electrode, or a porous ceramic, and have a relatively low temperature softening property, workability and workability. In addition, water resistance, weather resistance, and transparency are good, and a glass composition useful as an electrode support member for an electrochemical sensor has been investigated. However, no suitable glass composition that meets such requirements has been found.
Japanese Patent No. 3423673 Japanese Patent No. 3424700

従って、本発明の目的は、ガラス感応膜、白金電極などの感応部、或いは多孔質セラミックスとの熔着性が良く、比較的低温軟化性で加工性、細工性が良く、しかも耐水性、耐候性、透明性も良好なガラス組成物で形成された電気化学式センサの電極支持部材及び電気化学式センサを提供することである。   Therefore, the object of the present invention is to have good weldability with sensitive parts such as glass sensitive films, platinum electrodes, or porous ceramics, relatively low temperature softening property, good workability and workability, and water resistance and weather resistance. It is to provide an electrode support member for an electrochemical sensor and an electrochemical sensor formed of a glass composition having good properties and transparency.

本発明の他の目的は、電気化学式センサの製造過程での焼きなましなどの加熱処理による変色或いは着色を抑え、加工、細工が容易な電極支持部材及び電気化学式センサを提供することである。   Another object of the present invention is to provide an electrode support member and an electrochemical sensor that can be easily processed and crafted while suppressing discoloration or coloring due to heat treatment such as annealing in the manufacturing process of the electrochemical sensor.

上記目的は本発明に係る電極支持部材及び電気化学式センサにて達成される。要約すれば、第１の本発明は、電気化学式センサの電極支持部材において、重量百分率で、ＳｉＯ2 ６０〜７５％、Ｎａ2Ｏ ２〜１４％、Ｌｉ2Ｏ ０〜９％、Ｋ2Ｏ １〜９％（但し、Ｎａ2Ｏ＋Ｌｉ2Ｏ＋Ｋ2Ｏ １０〜２５％）、ＳｒＯ ０〜９％、ＣａＯ １〜９％、ＢａＯ １〜６％、ＭｇＯ ０〜６％、ＺｎＯ ０〜６％（但し、ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＭｇＯ＋ＺｎＯ １０〜２５％）、Ａｌ2Ｏ3 ０〜６％を含有するガラス組成物で形成された電極支持部材である。本発明の一実施態様によると、前記ガラス組成物の熱膨張係数（線膨張係数）は、９．４±２×１０-6／℃（３０℃〜８８０℃）である。又、本発明の一実施態様によると、前記ガラス組成物の軟化点は、９００℃以下である。ここで、本明細書において、ガラスの軟化点とは、ガラスの熔着が可能となる温度をいうものとする。本発明の一実施態様によると、前記電極支持部材には、多孔質セラミックスが熔着される。一実施態様では、前記電気化学式センサは、比較電極である。又、本発明の一実施態様によると、前記電極支持部材には、ガラス感応膜が熔着される。一実施態様では、前記電気化学式センサは、ｐＨ電極である。本発明の他の実施態様によると、白金電極が熔着される。一実施態様では、前記電気化学式センサは、電気伝導率セル、ＯＲＰ電極、ポーラログラフ式電極又はガルバニ式電極である。 The above object is achieved by the electrode support member and the electrochemical sensor according to the present invention. In summary, according to the first aspect of the present invention, in the electrode support member of an electrochemical sensor, SiO 2 60 to 75%, Na 2 O 2 to 14%, Li 2 O 0 to 9%, K 2 O in weight percentage. 1-9% (however, Na 2 O + Li 2 O + K 2 O 10~25%), SrO 0~9%, CaO 1~9%, BaO 1~6%, 0~6% MgO, 0~6% ZnO ( However, SrO + CaO + BaO + MgO + ZnO 10-25%) and an electrode support member formed of a glass composition containing Al 2 O 3 0-6%. According to an embodiment of the present invention, the glass composition has a thermal expansion coefficient (linear expansion coefficient) of 9.4 ± 2 × 10 −6 / ° C. (30 ° C. to 880 ° C.). Moreover, according to one embodiment of this invention, the softening point of the said glass composition is 900 degrees C or less. Here, in this specification, the softening point of glass shall mean the temperature at which glass can be welded. According to an embodiment of the present invention, porous ceramics are welded to the electrode support member. In one embodiment, the electrochemical sensor is a reference electrode. According to another embodiment of the present invention, a glass sensitive film is welded to the electrode support member. In one embodiment, the electrochemical sensor is a pH electrode. According to another embodiment of the invention, a platinum electrode is deposited. In one embodiment, the electrochemical sensor is an electrical conductivity cell, an ORP electrode, a polarographic electrode or a galvanic electrode.

第２の本発明によると、上記本発明の電極支持部材と、前記電極支持部材に熔着されたガラス感応膜と、を有することを特徴とする電気化学式センサが提供される。第２の本発明の一実施態様では、前記電極支持部材には更に、多孔質セラミックスが熔着される。   According to the second aspect of the present invention, there is provided an electrochemical sensor comprising the electrode support member of the present invention and a glass sensitive film welded to the electrode support member. In one embodiment of the second aspect of the present invention, porous ceramics are further welded to the electrode support member.

第３の本発明によると、上記本発明の電極支持部材と、前記電極支持部材に熔着された多孔質セラミックスと、を有することを特徴とする電気化学式センサが提供される。第２、第３の本発明の一実施態様によると、前記電気化学式センサは、ｐＨ電極であり、又、第３の本発明の一実施態様によると、前記電気化学式センサは比較電極である。   According to a third aspect of the present invention, there is provided an electrochemical sensor comprising the electrode support member of the present invention and a porous ceramic welded to the electrode support member. According to one embodiment of the second and third inventions, the electrochemical sensor is a pH electrode, and according to one embodiment of the third invention, the electrochemical sensor is a reference electrode.

第４の本発明によると、上記本発明の電極支持部材と、前記電極支持部材に熔着された白金電極と、を有することを特徴とする電気化学式センサが提供される。第４の本発明の一実施態様によると、前記電気化学式センサは、電気伝導率セル、ＯＲＰ電極、ポーラログラフ式電極又はガルバニ式電極である。又、第４の本発明の一実施態様によると、前記白金電極には無鉛半田にてリード線が接続され、当該電気化学式センサ外に導かれる。   According to a fourth aspect of the present invention, there is provided an electrochemical sensor comprising the electrode support member of the present invention and a platinum electrode welded to the electrode support member. According to an embodiment of the fourth invention, the electrochemical sensor is an electrical conductivity cell, an ORP electrode, a polarographic electrode or a galvanic electrode. According to an embodiment of the fourth aspect of the present invention, a lead wire is connected to the platinum electrode with lead-free solder and led out of the electrochemical sensor.

本発明の電極支持部材を構成するガラス組成を上記のように限定したのは次の理由による。   The reason why the glass composition constituting the electrode supporting member of the present invention is limited as described above is as follows.

ＳｉＯ2は、ガラス網目を形成する骨格成分であり、６０重量％より少ないとガラス化が困難となる。一方、７５重量％より多いと、ガラスの軟化する温度が高くなりすぎ、加工性、細工性が悪くなる。 SiO 2 is a skeletal component that forms a glass network, and if it is less than 60% by weight, vitrification becomes difficult. On the other hand, if it exceeds 75% by weight, the temperature at which the glass softens becomes too high, and the workability and workability deteriorate.

Ｎａ2Ｏ、Ｋ2Ｏはいずれも低温軟化性を増す効果がある。又、これらの成分は、熱膨張係数を高める。電極支持部材の加工性、細工性を考慮すると、ガラスの軟化点を９００℃以下にすることが好ましく、Ｎａ2Ｏは２重量％以上、Ｋ2Ｏは１重量％以上含有させる必要がある。一方、これらの成分は、多すぎると耐水性、耐候性を劣化させ、又熱膨張係数が大きくなり過ぎるため、Ｎａ2Ｏは１４重量％以下、Ｋ2Ｏは９重量％以下とする必要がある。 Both Na 2 O and K 2 O have the effect of increasing the low temperature softening property. These components also increase the coefficient of thermal expansion. Considering the workability and workability of the electrode support member, it is preferable that the softening point of the glass be 900 ° C. or lower, and Na 2 O should be contained in an amount of 2 % by weight or more and K 2 O should be contained in an amount of 1% by weight or more. On the other hand, if these components are too much, the water resistance and weather resistance are deteriorated, and the coefficient of thermal expansion becomes too large. Therefore, Na 2 O needs to be 14% by weight or less, and K 2 O needs to be 9% by weight or less. is there.

Ｌｉ2Ｏは、Ｎａ2Ｏ、Ｋ2Ｏと同様に、低温軟化性を増す効果があるが、Ｎａ2Ｏ、Ｋ2Ｏが上記の範囲で含まれる場合、９重量％以下にとどめる。これより多いと、耐水性、耐候性を劣化させ、又熱膨張係数が大きくなり過ぎる。 Li 2 O is, like the Na 2 O, K 2 O, is effective to increase the low-temperature softening property, if the Na 2 O, K 2 O is included within the above range, keep the 9 wt% or less. If it exceeds this range, the water resistance and weather resistance will be deteriorated, and the thermal expansion coefficient will become too large.

そして、低温軟化性を実現し、且つ、耐水性、耐候性を劣化させず、しかも熱膨張係数を大きくしすぎないように、上記Ｎａ2Ｏ、Ｋ2Ｏ、Ｌｉ2Ｏは、合計量で１０〜２５重量％の範囲で含まれていることが必要である。 The Na 2 O, K 2 O, and Li 2 O are added in a total amount so as to realize low-temperature softening properties and not deteriorate the water resistance and weather resistance and increase the thermal expansion coefficient too much. It is necessary to be contained in the range of 10 to 25% by weight.

ＳｒＯは、ガラス網目修飾酸化物であり、耐水性、耐候性の向上に効果的で、適量は失透防止や、加工性改善に役立つ。又、ＳｒＯは、熱膨張係数を高める。ＣａＯ、ＢａＯが下記の範囲で含まれる場合、９重量％以下にとどめる必要があり、これより多いと、失透の原因や気泡抜けが悪くなり、又熱膨張係数を大きくし過ぎる。   SrO is a glass network-modifying oxide, and is effective in improving water resistance and weather resistance. An appropriate amount is useful for preventing devitrification and improving workability. SrO also increases the thermal expansion coefficient. When CaO and BaO are included in the following ranges, it is necessary to keep them at 9% by weight or less. If the CaO and BaO are included in the following range, the cause of devitrification and the loss of bubbles deteriorate, and the thermal expansion coefficient becomes too large.

ＣａＯ、ＢａＯは、上記ＳｒＯと同様に、ガラス網目修飾酸化物であり、耐水性、耐候性の向上に効果的で、適量は失透防止や、加工性改善に役立つ。又、これらの成分は、熱膨張係数を高める。所望の効果を得るためには、ＣａＯは１重量％以下、ＢａＯは１重量％以上が必要である。一方、これらの成分は、多すぎると失透の原因や気泡抜けが悪くなり、又熱膨張係数を大きくし過ぎるため、ＣａＯは９重量％以下、ＢａＯは６重量％以下とする必要がある。   Similar to SrO, CaO and BaO are glass network-modified oxides, which are effective for improving water resistance and weather resistance, and appropriate amounts are useful for preventing devitrification and improving workability. These components also increase the coefficient of thermal expansion. In order to obtain a desired effect, CaO is required to be 1% by weight or less, and BaO is required to be 1% by weight or more. On the other hand, if these components are too large, the cause of devitrification and bubble removal will be poor, and the coefficient of thermal expansion will be too large, so CaO must be 9 wt% or less and BaO must be 6 wt% or less.

ＭｇＯは、加工性の向上に役立つが、多すぎると耐候性、耐水性を弱めるため、６重量％以下とする。又、ＭｇＯは、熱膨張係数にあまり影響しない。   MgO is useful for improving the workability, but if it is too much, the weather resistance and water resistance are weakened. MgO does not significantly affect the thermal expansion coefficient.

ＺｎＯは、軟化点を下げる効果がある。又、ＺｎＯは、熱膨張係数を下げる。これが多すぎると、耐水性を弱めるため、６重量％以下とする。   ZnO has the effect of lowering the softening point. ZnO also lowers the thermal expansion coefficient. If this is too much, the water resistance is weakened, so it is made 6% by weight or less.

但し、耐水性、耐候性を向上すると共に、失透を防止し、加工性を改善し、熱膨張係数を所望の範囲とするためには、上記ＳｒＯ、ＣａＯ、ＢａＯ、ＭｇＯ、ＺｎＯの合計量が１０〜２５重量％の範囲とするのが好適である。２５重量％を超えると、耐候性、耐水性を弱めるため、１０重量％より少ないと十分な効果が得られない。   However, in order to improve water resistance and weather resistance, prevent devitrification, improve workability, and make the thermal expansion coefficient within a desired range, the total amount of SrO, CaO, BaO, MgO, ZnO Is preferably in the range of 10 to 25% by weight. If it exceeds 25% by weight, the weather resistance and water resistance will be weakened, and if it is less than 10% by weight, sufficient effects cannot be obtained.

Ａｌ2Ｏ3は、少量の含有は失透を抑え、耐水性、耐候性を上げるのに効果的だが、多すぎると低温軟化性を阻害するため、６重量％以下とする必要がある。Ａｌ2Ｏ3は、熱膨張係数にはあまり影響しない。 A small amount of Al 2 O 3 is effective for suppressing devitrification and improving water resistance and weather resistance, but if it is too much, low temperature softening property is inhibited, so 6% by weight or less is necessary. Al 2 O 3 does not significantly affect the thermal expansion coefficient.

本発明によれば、電極支持部材は、ガラス感応膜、白金電極などの感応部、或いは多孔質セラミックスとの熔着性が良く、比較的低温軟化性で加工性、細工性が良い。又、本発明によれば、電極支持部材及び電気化学式センサは、耐水性、耐候性、透明性も良好である。更に、本発明によれば、電極支持部材及び電気化学式センサは、製造過程での焼きなましなどの加熱処理による変色或いは着色が抑えられ、加工、細工が容易である。   According to the present invention, the electrode support member has good weldability with a sensitive part such as a glass sensitive film, a platinum electrode, or porous ceramics, and has relatively low temperature softening properties and good workability and workability. Further, according to the present invention, the electrode support member and the electrochemical sensor have good water resistance, weather resistance, and transparency. Furthermore, according to the present invention, the electrode support member and the electrochemical sensor are prevented from being discolored or colored by heat treatment such as annealing in the manufacturing process, and are easy to process and work.

以下、本発明に係る電極支持部材を実施例により更に説明する。   Hereinafter, the electrode support member according to the present invention will be further described with reference to examples.

実施例１
本発明に係る電極保持部材を用いてｐＨ電極を作製し、熔着性、加工性等について検討した。図１に、本発明に係る電気化学式センサであるｐＨ電極の一実施例を示す。本実施例によると、ｐＨ電極１００は、電極支持部材として、内管１１と外管１２との先端部１３を互いに一体に熱熔接により封止した二重ガラス管とされる支持管１を有する。更に、この支持管１の先端部１３に、ｐＨに感応するガラス感応膜（ｐＨ感応膜）２Ａが一体に接合されている。 Example 1
A pH electrode was prepared using the electrode holding member according to the present invention, and the weldability, workability, and the like were examined. FIG. 1 shows an embodiment of a pH electrode which is an electrochemical sensor according to the present invention. According to the present embodiment, the pH electrode 100 has a support tube 1 that is a double glass tube in which the tip portions 13 of the inner tube 11 and the outer tube 12 are integrally sealed with each other by heat welding as an electrode support member. . Further, a glass sensitive membrane (pH sensitive membrane) 2A sensitive to pH is integrally joined to the tip 13 of the support tube 1.

そして、ｐＨ電極１００は、従来と同様に、内管１１中に測定電極内極１４が配置され、測定電極内部液が充填される。又、内管１１と外管１２とにて形成された環状空間部には比較電極内極１５が配置され、比較電極内部液が充填される。内管１１、ガラス感応膜２Ａ、内部電極１４などでｐＨ測定電極が形成され、外管１２、比較電極内極１５などで比較電極が形成される。本実施例では、ｐＨ電極１００は、これら測定電極及び比較電極が一体とされた複合電極である。   In the pH electrode 100, the measurement electrode inner electrode 14 is disposed in the inner tube 11 and filled with the measurement electrode internal liquid, as in the conventional case. A reference electrode inner electrode 15 is disposed in the annular space formed by the inner tube 11 and the outer tube 12 and filled with the solution inside the reference electrode. The inner tube 11, the glass sensitive film 2A, the inner electrode 14 and the like form a pH measurement electrode, and the outer tube 12 and the comparison electrode inner electrode 15 and the like form a comparison electrode. In this embodiment, the pH electrode 100 is a composite electrode in which the measurement electrode and the comparison electrode are integrated.

更に、外管１２の下方部に、多孔質セラミックスで形成されたジャンクション（液絡部）２Ｂが封入され、外管１２とｐＨ電極１００外の被検液との間の電気的導通が可能とされる。   Furthermore, a junction (liquid junction part) 2B formed of porous ceramics is enclosed in the lower part of the outer tube 12, and electrical connection between the outer tube 12 and the test solution outside the pH electrode 100 is possible. Is done.

尚、ここでは、支持管１は内管１１と外管１２とを備える二重ガラス管であるが、当然、支持管１は単管でもよく、測定電極単体のｐＨ電極とすることも当然可能である。一方、電極支持部材としての支持管（単管）にジャンクション２Ｂを設けた単体の比較電極を構成することもできる。本明細書では、単体の比較電極をも含み電気化学式センサという。ｐＨ電極自体については、当業者に周知であり、その具体的構成は本発明にとって任意であるのでこれ以上の説明は省略する。   Here, the support tube 1 is a double glass tube provided with an inner tube 11 and an outer tube 12, but naturally the support tube 1 may be a single tube or a pH electrode as a single measurement electrode. It is. On the other hand, a single comparison electrode in which a junction 2B is provided on a support tube (single tube) as an electrode support member can also be configured. In this specification, an electrochemical sensor including a single reference electrode is also referred to. The pH electrode itself is well known to those skilled in the art, and the specific configuration thereof is arbitrary for the present invention, so that further explanation is omitted.

ｐＨ電極１００の製造方法は従来のものと変わりないので、詳しい説明は省略するが、一例を示せば概略次の通りである。先ず、熔融ガラス（ガラス膜種）を収容した坩堝を炉（電気炉）内に設置し、その上方所定位置に、支持管１をセットする。   Since the manufacturing method of the pH electrode 100 is not different from the conventional one, detailed description is omitted, but an example is as follows. First, a crucible containing molten glass (glass film type) is installed in a furnace (electric furnace), and the support tube 1 is set at a predetermined position above the crucible.

ガラス膜種は、作製するｐＨ電極１００の用途に応じて、主成分として次の組成のガラスを使用することができる。（ａ）標準用：ＳｉＯ2、Ｌｉ2Ｏ、Ｃｓ2ＣＯ3、ＢａＣＯ3、ＴｉＯ2、Ｌａ2Ｏ3（ｂ）アルカリ用：ＳｉＯ2、Ｌｉ2Ｏ、Ｃｅ2ＣＯ3、Ｌａ2Ｏ3、Ｐｒ2Ｏ3（ｃ）耐フッ酸用：ＳｉＯ2、Ｌｉ2Ｏ、ＢａＣＯ3、Ｔａ2Ｏ5、Ｃｒ2Ｏ3、Ｌａ2Ｏ3（ｄ）発酵用：ＳｉＯ2、Ｌｉ2Ｏ、ＢａＣＯ3、ＴｉＯ2、Ｌａ2Ｏ3。これらＬｉ系ガラスのガラス膜種の熱膨張係数は、８〜１０．５×１０-6／℃の範囲内にある。 As the glass film type, glass having the following composition can be used as a main component depending on the application of the pH electrode 100 to be produced. (A) For standard: SiO 2 , Li 2 O, Cs 2 CO 3 , BaCO 3 , TiO 2 , La 2 O 3 (b) For alkali: SiO 2 , Li 2 O, Ce 2 CO 3 , La 2 O 3 Pr 2 O 3 (c) For hydrofluoric acid resistance: SiO 2 , Li 2 O, BaCO 3 , Ta 2 O 5 , Cr 2 O 3 , La 2 O 3 (d) For fermentation: SiO 2 , Li 2 O, BaCO 3 , TiO 2 , La 2 O 3 . The thermal expansion coefficient of the glass film type of these Li-based glasses is in the range of 8 to 10.5 × 10 −6 / ° C.

坩堝の炉内温度を適温（例えば、１０００〜１５５０℃）に調整して、坩堝を所定時間加熱し、その後、支持管１を適当な速度（例えば、１００〜５００ｍｍ／ｓｅｃ）にて降下させ、支持管１の先端を坩堝のガラス膜種中に浸漬する。支持管１の先端が浸漬された坩堝は、炉内温度を調整して適温（例えば、１０００〜１５５０℃）とし、坩堝を所定時間加熱しながら支持管１の先端にガラス膜種を付着させる。次いで、ガラス膜種が付着した支持管１を上方へと適当な速度（例えば、５００〜１５００ｍｍ／ｓｅｃ）にて引き上げ、引き続いて、支持管１にエアーを吹き込み、支持管１の先端に付着したガラス膜種を半球状に膨らませてガラス感応膜２Ａを形成する。   The furnace temperature of the crucible is adjusted to an appropriate temperature (for example, 1000 to 1550 ° C.), the crucible is heated for a predetermined time, and then the support tube 1 is lowered at an appropriate speed (for example, 100 to 500 mm / sec), The tip of the support tube 1 is immersed in the glass film seed of the crucible. The crucible in which the tip of the support tube 1 is immersed is adjusted to an appropriate temperature (for example, 1000 to 1550 ° C.) by adjusting the furnace temperature, and the glass film seed is attached to the tip of the support tube 1 while heating the crucible for a predetermined time. Next, the support tube 1 to which the glass film seed is adhered is pulled upward at an appropriate speed (for example, 500 to 1500 mm / sec), and then air is blown into the support tube 1 to adhere to the tip of the support tube 1. The glass sensitive film 2A is formed by expanding the glass film seed into a hemispherical shape.

尚、ジャンクション２Ｂは、例えば、直径約１ｍｍの略円柱状多孔質セラミックスを、約３ｍｍの長さに切断し、加熱により支持管１に開いた孔に配置して封入する。   For example, the junction 2B is formed by cutting a substantially cylindrical porous ceramic having a diameter of about 1 mm into a length of about 3 mm, and placing it in a hole opened in the support tube 1 by heating.

支持管１のガラス組成を下記表１に示す。具体例１及び具体例２のガラスで作製された支持管１、これを用いて作製したｐＨ電極１００は、本発明に従う。比較のために、比較例１として、従来の鉛ガラスで作製された支持管１を用いてｐＨ電極１００を作製した。   The glass composition of the support tube 1 is shown in Table 1 below. The support tube 1 made of the glass of the specific example 1 and the specific example 2, and the pH electrode 100 made using the same are in accordance with the present invention. For comparison, as Comparative Example 1, a pH electrode 100 was produced using a support tube 1 made of conventional lead glass.

Figure 2005207887
Figure 2005207887

具体例１及び具体例２のガラスで作製された支持管１は、ガラス感応膜２を熔着してｐＨ電極１００を作製するのに適していることが分かった。具体例１及び具体例２のガラスはいずれも軟化点は９００℃以下であり、加工性、細工性は、従来の鉛ガラス製の支持管１を用いた場合と同等に良好で、ガラス感応膜２Ａの付着性も良好であることが確認された。   It was found that the support tube 1 made of the glass of the specific example 1 and the specific example 2 is suitable for manufacturing the pH electrode 100 by welding the glass sensitive film 2. The glass of Specific Example 1 and Specific Example 2 both have a softening point of 900 ° C. or less, and the workability and workability are as good as when the conventional lead glass support tube 1 is used. It was confirmed that the adhesion of 2A was also good.

又、作製されたｐＨ電極１００は、通常使用温度（０〜１００℃）において、温度変化によって支持管１とガラス感応膜２との熔着部、又支持管１とジャンクション２Ｂとの熔着部にクラックなどの破損が発生しないことが確認された。   The produced pH electrode 100 has a welded portion between the support tube 1 and the glass sensitive film 2 and a welded portion between the support tube 1 and the junction 2B due to temperature change at a normal use temperature (0 to 100 ° C.). It was confirmed that no damage such as cracks occurred.

更に、支持管１の先端部１３を熱熔接する際に、変色、着色などは見られなかった。比較例１の鉛ガラスにて作製された支持管１において、若干通常より多く炙ることで鉛色に着色するのと同程度に、具体例１及び具体例２のガラスにて作製された支持管１を炙ったが、依然変色、着色は見られなかった。本発明によれば、支持管１は従来の鉛ガラスと比較して、電気化学式センサの製造工程における変色、着色に強く、加工、細工が容易であることが分かった。   Further, no discoloration or coloring was observed when the tip 13 of the support tube 1 was heat welded. In the support tube 1 made of the lead glass of the comparative example 1, the support tube made of the glass of the specific example 1 and the specific example 2 to the same extent that it is colored in a lead color by slightly more than usual. No. 1 was given, but no discoloration or coloring was observed. According to the present invention, it was found that the support tube 1 is more resistant to discoloration and coloring in the manufacturing process of the electrochemical sensor than the conventional lead glass, and is easy to process and work.

実施例２
本発明に係る電極保持部材を用いてポーラロ式電極を作製し、熔着性、加工性等について検討した。図２に、本発明に係る電気化学式センサであるポーラログラフ式電極であるポーラログラフ式隔膜型電極２００（以下、単に「ポーラログラフ式電極」という。）を示す。図示するように、ポーラログラフ式電極２００は、電極支持部材としてガラスにて作製された支持管１を有し、その先端に作用極としての金属極たる白金電極２Ｃが熔着され、又、支持管１の外周部に、更に対極１６が取り付けられる。一般に、対極１６としては、銀（Ａｇ）、銀−塩化銀（Ａｇ／ＡｇＣｌ）が用いられる。支持管１を囲包して中空円筒状の外筒１８が設けられ、その先端開口部に、白金電極２Ｃに近接して、ガス透過性隔膜１７が固定される。そして、支持管１と外筒１８と隔膜１７とで区画された空間内には、電解液が収容される。 Example 2
Polaro-type electrodes were prepared using the electrode holding member according to the present invention, and the weldability, workability, and the like were examined. FIG. 2 shows a polarographic diaphragm-type electrode 200 (hereinafter simply referred to as “polarographic electrode”) that is a polarographic electrode that is an electrochemical sensor according to the present invention. As shown in the figure, a polarographic electrode 200 has a support tube 1 made of glass as an electrode support member, and a platinum electrode 2C as a working electrode is welded to the tip of the support tube 1, and the support tube A counter electrode 16 is further attached to the outer peripheral portion of 1. In general, silver (Ag) or silver-silver chloride (Ag / AgCl) is used as the counter electrode 16. A hollow cylindrical outer cylinder 18 is provided so as to surround the support tube 1, and a gas permeable diaphragm 17 is fixed to an opening portion of the hollow cylinder 18 adjacent to the platinum electrode 2 </ b> C. An electrolytic solution is accommodated in a space defined by the support tube 1, the outer cylinder 18, and the diaphragm 17.

白金電極２Ｃ及び対極１６にはそれぞれ白金或いは銀とされるリード線１９ａ、１９ｂが接続され、これらリード線１９ａ、１９ｂは支持管１内を通って外部に導出され、電圧印加手段（図示せず）に接続される。又、隔膜１７を透過した測定対象ガスを、白金電極２Ｃの面で反応させ、そのとき白金電極２Ｃに流れる溶存ガスの電解電流を電流計（図示せず）で測定するようになっている。好ましくは、環境配慮の観点から、リード線１９ａ、１９ｂは、無鉛半田にて各極２Ｃ、１６に接続し、電極外部へと導く（リードアウト）ことが好ましい。ポーラログラフ式電極自体については、当業者に周知であり、その具体的構成は本発明にとって任意であるのでこれ以上の説明は省略する。   Lead wires 19a and 19b made of platinum or silver are connected to the platinum electrode 2C and the counter electrode 16, respectively, and these lead wires 19a and 19b are led out to the outside through the support tube 1, and voltage applying means (not shown). ). Further, the gas to be measured that has passed through the diaphragm 17 is reacted on the surface of the platinum electrode 2C, and the electrolytic current of the dissolved gas flowing through the platinum electrode 2C at that time is measured with an ammeter (not shown). Preferably, from the viewpoint of environmental consideration, the lead wires 19a and 19b are preferably connected to the respective electrodes 2C and 16 with lead-free solder and led out of the electrodes (lead out). The polarographic electrode itself is well known to those skilled in the art, and its specific configuration is arbitrary for the present invention, and thus further description thereof is omitted.

ポーラログラフ式電極２００の製造方法は従来のものと変わりないので、詳しい説明は省略するが、特に、支持管１に白金電極２Ｃを熔着させる方法の一例を示せば、概略次の通りである。   Since the manufacturing method of the polarographic electrode 200 is the same as the conventional method, detailed description is omitted. In particular, if an example of the method of welding the platinum electrode 2C to the support tube 1 is shown, it is as follows.

支持管１の一端部を加熱して試験管様に閉じた後、開放した他端から空気を吹き込みながら、閉じた一端の一部を細い炎で加熱し、下記白金線２Ｃ２が入る孔を開ける。一方、厚さ約０．１５ｍｍ、直径約１０ｍｍの白金板２Ｃ１の中央に、直径約０．５ｍｍ、長さ約１０ｍｍの白金線２Ｃ２をスポット溶接する。そして、この白金線２Ｃ２を、支持管１の端部に上述のようにして開けた孔に差し込み、所定の位置に取り付けて全体を炎で炙って、支持管１と白金をなじませながら白金をガラスに封入する。白金板２Ｃ１の白金線２Ｃ２がスポット溶接されていない側の端面を、支持管１の面（外面）から露出するようにし、又白金線２Ｃ２は、無鉛半田３０により半田付けしてリード線１９ａに接続する。   After one end of the support tube 1 is heated and closed like a test tube, a part of the closed end is heated with a thin flame while blowing air from the other open end, and a hole for receiving the following platinum wire 2C2 is opened. . On the other hand, a platinum wire 2C2 having a diameter of about 0.5 mm and a length of about 10 mm is spot welded to the center of a platinum plate 2C1 having a thickness of about 0.15 mm and a diameter of about 10 mm. Then, the platinum wire 2C2 is inserted into the hole formed in the end portion of the support tube 1 as described above, attached to a predetermined position, and the whole is burned with a flame, and platinum is mixed with the support tube 1 and platinum. Enclose in glass. The end surface of the platinum plate 2C1 on the side where the platinum wire 2C2 is not spot welded is exposed from the surface (outer surface) of the support tube 1, and the platinum wire 2C2 is soldered to the lead wire 19a by lead-free solder 30. Connecting.

実施例１と同様、表１に示す具体例１及び具体例２のガラスで作製された支持管１を用いてポーラログラフ式電極２００を作製した。又、比較のために、比較例１に示す組成の鉛ガラスで作製された支持管１でポーラログラフ式電極２００を作製した。   Similarly to Example 1, a polarographic electrode 200 was produced using the support tube 1 made of the glass of Specific Example 1 and Specific Example 2 shown in Table 1. For comparison, a polarographic electrode 200 was prepared using a support tube 1 made of lead glass having the composition shown in Comparative Example 1.

その結果、具体例１及び具体例２のガラスで作製された支持管１は、白金電極を熔着してポーラログラフ式電極２００を作製するのに適していることが分かった。又、加工性、細工性は、従来の鉛ガラス製の支持管１を用いた場合と同等に良好であることが確認された。又、作製されたポーラログラフ式電極２００は、通常使用温度（０〜５０℃）において、温度変化によって支持管１と白金電極との熔着部にクラックなどの破損が発生しないことが確認された。   As a result, it was found that the support tube 1 made of the glass of specific example 1 and specific example 2 is suitable for producing a polarographic electrode 200 by welding a platinum electrode. Moreover, it was confirmed that workability and workability were as good as when the conventional lead glass support tube 1 was used. Moreover, it was confirmed that the produced polarographic electrode 200 does not cause breakage such as cracks in the welded portion between the support tube 1 and the platinum electrode due to temperature change at normal operating temperature (0 to 50 ° C.).

尚、上記では、ポーラログラフ式電極２００の支持管１に本発明を適用したが、当業者は、ガルバニ式電極（ガルバニ電池式隔膜型電極など）など、ガラス製の電極支持部材に白金電極を熔着する他の任意の電気化学式センサに対して等しく適用可能である。   In the above description, the present invention is applied to the support tube 1 of the polarographic electrode 200. However, those skilled in the art can melt a platinum electrode on a glass electrode support member such as a galvanic electrode (galvanic cell type diaphragm electrode or the like). It is equally applicable to any other electrochemical sensor that wears.

ガルバニ式電極は、ポーラログラフ式電極２００と概略同様の構成であるが、作用極としての白金電極と、鉛（Ｐｂ）、カドミウム（Ｃｄ）などから成る対極との間に電圧を印加する電圧印加手段（電源）を有していないことが異なる。ガルバニ式電極自体については、当業者に周知であり、その具体的構成は本発明にとって任意であるのでこれ以上の説明は省略する。   The galvanic electrode has substantially the same configuration as the polarographic electrode 200, but a voltage applying means for applying a voltage between a platinum electrode as a working electrode and a counter electrode made of lead (Pb), cadmium (Cd), or the like. The difference is that it does not have (power). The galvanic electrode itself is well known to those skilled in the art, and the specific configuration thereof is arbitrary for the present invention, so that further explanation is omitted.

又、ＯＲＰ電極は、本発明に従う電極支持部材を使用して白金電極を作製し、比較電極と組み合わせてＯＲＰ電極とする。ＯＲＰ電極の製造方法に関しても、従来のものと変わりなく、特に、白金電極を熔着させる方法は、上記と同様にすればよい。一例を示せば、厚さ約０．１５ｍｍ、直径約１０ｍｍの白金板の中央に、直径約０．５ｍｍ、長さ約１０ｍｍの白金線をスポット溶接して、白金線がスポット溶接された白金板の一端面と、白金線とを、電極支持部材たる支持管に封入し、白金板の白金線がスポット溶接されていない側の端面がガラス面から露出するようにし、更に封入した白金線のスポット溶接していない反対側にリード線を無鉛半田で半田付けして接続する。   The ORP electrode is made of a platinum electrode using the electrode support member according to the present invention, and combined with the comparison electrode to form an ORP electrode. The method for manufacturing the ORP electrode is not different from the conventional one, and in particular, the method for welding the platinum electrode may be the same as described above. For example, a platinum plate having a platinum wire spot-welded by spot welding a platinum wire having a diameter of about 0.5 mm and a length of about 10 mm in the center of a platinum plate having a thickness of about 0.15 mm and a diameter of about 10 mm. One end face of the metal plate and a platinum wire are sealed in a support tube as an electrode support member so that the end face of the platinum plate on which the platinum wire is not spot-welded is exposed from the glass surface. Solder the lead wire with lead-free solder to the other side that is not welded.

更に、電気伝導率セルは、図３に示すように、電極支持部材として、端部支持管１ａと、基部支持管１ｂとが一体的にされた支持管１を有し、開放した端部２１を有する端部支持管１ａに設けられた、例えば２つの白金電極２Ｄ、２Ｄ間に交流を流して、両極間の空間に導入された被検液のインピーダンスを計測することで、被検液の電気伝導率を計測するようになっている。又、端部支持管１ａには、気泡抜き穴２３を設けることができる。電気伝導率セル３００の製造方法は従来のものと変わりないので、詳しい説明は省略するが、特に、白金電極２Ｄを熔着させる方法の一例を示せば、概略次の通りである。尚、白金電極２Ｄを２つ設ける場合、両電極について同様にして熔着させることができる。   Further, as shown in FIG. 3, the electrical conductivity cell has a support tube 1 in which an end support tube 1a and a base support tube 1b are integrated as an electrode support member, and an open end 21 is provided. For example, by passing an alternating current between the two platinum electrodes 2D and 2D and measuring the impedance of the test liquid introduced into the space between the two electrodes, Electrical conductivity is measured. Further, the end support tube 1a can be provided with a bubble removal hole 23. Since the manufacturing method of the electrical conductivity cell 300 is not different from the conventional method, a detailed description is omitted. In particular, an example of a method of welding the platinum electrode 2D is as follows. When two platinum electrodes 2D are provided, both electrodes can be welded in the same manner.

厚さ約０．１５ｍｍ、直径約１０ｍｍの白金板２Ｄ１の中央に、直径約０．５ｍｍ、長さ約１０ｍｍの白金線２Ｄ２をスポット溶接したものを、白金線２Ｄ２がスポット溶接された白金板２Ｄ１の一端面と、白金線２Ｄ２の一部とを、端部支持管１ａに封入する。そして、白金板２Ｄ１の白金線２Ｄ２がスポット溶接されていない側の端面が、端部支持管１ａのガラス面（管内面）から露出するようにする。又、白金線２Ｄ２の、白金板２Ｄ１とのスポット溶接部とは反対側の、端部支持管１ａに封入されていない端部に、リード線２４を無鉛半田３０により半田付けして接続する。次いで、端部支持管１ａの底部２２側に、端部支持管１ａと略同径の基部支持管１ｂを熔着する。   A platinum plate 2D1 obtained by spot welding a platinum wire 2D2 having a diameter of about 0.5 mm and a length of about 10 mm at the center of a platinum plate 2D1 having a thickness of about 0.15 mm and a diameter of about 10 mm. And one end surface of the platinum wire 2D2 are enclosed in the end support tube 1a. Then, the end surface of the platinum plate 2D1 on the side where the platinum wire 2D2 is not spot welded is exposed from the glass surface (tube inner surface) of the end support tube 1a. Further, the lead wire 24 is soldered and connected with the lead-free solder 30 to the end of the platinum wire 2D2 opposite to the spot welded portion with the platinum plate 2D1 and not sealed in the end support tube 1a. Next, a base support tube 1b having the same diameter as the end support tube 1a is welded to the bottom 22 side of the end support tube 1a.

尚、電気伝導率セルは、白金板の中央に白金線をスポット溶接し、白金線の白金板にスポット溶接された一端部とは反対側の端部付近を電極支持管に封入して、この端部にリード線を無鉛半田で半田付けして接続した電極と、これと同じ構造の電極との間に交流を流すように構成することもできる。   In the electrical conductivity cell, a platinum wire is spot-welded in the center of the platinum plate, and an end portion of the platinum wire opposite to the one end portion spot-welded to the platinum plate is sealed in an electrode support tube. It is also possible to configure so that an alternating current flows between an electrode in which a lead wire is soldered and connected to the end portion with lead-free solder and an electrode having the same structure.

以上、本発明によれば、支持管１は、ガラス感応膜２Ａ、白金電極２Ｃなどの感応部、或いは多孔質セラミックスのジャンクション２Ｂとの熔着性が良く、比較的低温軟化性で加工性、細工性が良い。又、支持管１及び電気化学式センサは、耐水性、耐候性、透明性も良好である。更に、支持管１及び電気化学式センサは、製造過程での焼きなましなどの加熱処理による変色或いは着色が抑えられ、加工、細工が容易である。   As described above, according to the present invention, the support tube 1 has good weldability with the sensitive part such as the glass sensitive film 2A, the platinum electrode 2C, or the junction 2B of the porous ceramics, and is relatively low temperature softening and workability. Good workability. Further, the support tube 1 and the electrochemical sensor have good water resistance, weather resistance, and transparency. Further, the support tube 1 and the electrochemical sensor can be easily processed and crafted, since discoloration or coloring due to heat treatment such as annealing in the manufacturing process is suppressed.

本発明を適用し得るｐＨ電極の一例の要部概略断面図である。It is a principal part schematic sectional drawing of an example of the pH electrode which can apply this invention. 本発明を適用し得るポーラログラフ式電極の要部を示す模式図である。It is a schematic diagram which shows the principal part of the polarographic electrode which can apply this invention. 本発明を適用し得る電気伝導率セルの一例の要部概略断面図である。It is a principal part schematic sectional drawing of an example of the electrical conductivity cell which can apply this invention.

符号の説明Explanation of symbols

１ 支持管（電極支持部材）
２Ａ ガラス感応膜
２Ｂ ジャンクション
２Ｃ、２Ｄ 白金電極 1 Support tube (electrode support member)
2A Glass sensitive film 2B Junction 2C, 2D Platinum electrode

Claims (19)

電気化学式センサの電極支持部材において、重量百分率で、ＳｉＯ2 ６０〜７５％、Ｎａ2Ｏ ２〜１４％、Ｌｉ2Ｏ ０〜９％、Ｋ2Ｏ １〜９％（但し、Ｎａ2Ｏ＋Ｌｉ2Ｏ＋Ｋ2Ｏ １０〜２５％）、ＳｒＯ ０〜９％、ＣａＯ １〜９％、ＢａＯ １〜６％、ＭｇＯ ０〜６％、ＺｎＯ ０〜６％（但し、ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＭｇＯ＋ＺｎＯ １０〜２５％）、Ａｌ2Ｏ3 ０〜６％を含有するガラス組成物で形成された電極支持部材。 In the electrode support member of the electrochemical sensor, in terms of weight percentage, SiO 2 60 to 75%, Na 2 O 2 to 14%, Li 2 O 0 to 9%, K 2 O 1 to 9% (however, Na 2 O + Li 2 O + K 2 O 10-25%), SrO 0-9%, CaO 1-9%, BaO 1-6%, MgO 0-6%, ZnO 0-6% (however, SrO + CaO + BaO + MgO + ZnO 10-25%), Al 2 O 3 Less than six% of the electrode support member formed of a glass composition containing. 前記ガラス組成物の熱膨張係数（線膨張係数）は、９．４±２×１０-6／℃であることを特徴とする請求項１の電極支持部材。 2. The electrode support member according to claim 1, wherein the glass composition has a thermal expansion coefficient (linear expansion coefficient) of 9.4 ± 2 × 10 −6 / ° C. 3. 前記ガラス組成物の軟化点は、９００℃以下であることを特徴とする請求項１又は２の電極支持部材。   The electrode support member according to claim 1, wherein the glass composition has a softening point of 900 ° C. or lower. 多孔質セラミックスが熔着されることを特徴とする請求項１〜３のいずれかの項に記載の電極支持部材。   The electrode supporting member according to any one of claims 1 to 3, wherein porous ceramics are welded. ガラス感応膜が熔着されることを特徴とする請求項１〜４のいずれかの項に記載の電極支持部材。   The electrode supporting member according to any one of claims 1 to 4, wherein a glass sensitive film is welded. 前記電気化学式センサは、ｐＨ電極であることを特徴とする請求項４又は５の電極支持部材。   6. The electrode support member according to claim 4, wherein the electrochemical sensor is a pH electrode. 前記電気化学センサは、比較電極であることを特徴とする請求項４の電極支持部材。   The electrode support member according to claim 4, wherein the electrochemical sensor is a reference electrode. 白金電極が熔着されることを特徴とする請求項１〜３のいずれかの項に記載の電極支持部材。   The electrode support member according to any one of claims 1 to 3, wherein a platinum electrode is welded. 前記電気化学式センサは、電気伝導率セル、ＯＲＰ電極、ポーラログラフ式電極又はガルバニ式電極であることを特徴とする請求項８の電極支持部材。   9. The electrode support member according to claim 8, wherein the electrochemical sensor is an electrical conductivity cell, an ORP electrode, a polarographic electrode, or a galvanic electrode. 重量百分率で、ＳｉＯ2 ６０〜７５％、Ｎａ2Ｏ ２〜１４％、Ｌｉ2Ｏ ０〜９％、Ｋ2Ｏ １〜９％（但し、Ｎａ2Ｏ＋Ｌｉ2Ｏ＋Ｋ2Ｏ １０〜２５％）、ＳｒＯ ０〜９％、ＣａＯ １〜９％、ＢａＯ １〜６％、ＭｇＯ ０〜６％、ＺｎＯ ０〜６％（但し、ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＭｇＯ＋ＺｎＯ １０〜２５％）、Ａｌ2Ｏ3 ０〜６％を含有するガラス組成物で形成された電極支持部材と、前記電極支持部材に熔着されたガラス感応膜と、を有することを特徴とする電気化学式センサ。 In weight percent, SiO 2 60~75%, Na 2 O 2~14%, Li 2 O 0~9%, K 2 O 1~9% ( however, Na 2 O + Li 2 O + K 2 O 10~25%), Contains SrO 0-9%, CaO 1-9%, BaO 1-6%, MgO 0-6%, ZnO 0-6% (however, SrO + CaO + BaO + MgO + ZnO 10-25%), Al 2 O 3 0-6% An electrochemical sensor, comprising: an electrode support member formed of a glass composition; and a glass sensitive film welded to the electrode support member. 前記電極支持部材には更に、多孔質セラミックスが熔着されることを特徴とする請求項１０の電気化学式センサ。   The electrochemical sensor according to claim 10, wherein porous ceramics are further welded to the electrode support member. 重量百分率で、ＳｉＯ2 ６０〜７５％、Ｎａ2Ｏ ２〜１４％、Ｌｉ2Ｏ ０〜９％、Ｋ2Ｏ １〜９％（但し、Ｎａ2Ｏ＋Ｌｉ2Ｏ＋Ｋ2Ｏ １０〜２５％）、ＳｒＯ ０〜９％、ＣａＯ １〜９％、ＢａＯ １〜６％、ＭｇＯ ０〜６％、ＺｎＯ ０〜６％（但し、ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＭｇＯ＋ＺｎＯ １０〜２５％）、Ａｌ2Ｏ3 ０〜６％を含有するガラス組成物で形成された電極支持部材と、前記電極支持部材に熔着された多孔質セラミックスと、を有することを特徴とする電気化学式センサ。 In weight percent, SiO 2 60~75%, Na 2 O 2~14%, Li 2 O 0~9%, K 2 O 1~9% ( however, Na 2 O + Li 2 O + K 2 O 10~25%), Contains SrO 0-9%, CaO 1-9%, BaO 1-6%, MgO 0-6%, ZnO 0-6% (however, SrO + CaO + BaO + MgO + ZnO 10-25%), Al 2 O 3 0-6% An electrochemical sensor comprising: an electrode support member formed of a glass composition; and porous ceramics welded to the electrode support member. ｐＨ電極であることを特徴とする請求項１０、１１又は１２の電気化学式センサ。   The electrochemical sensor according to claim 10, 11 or 12, which is a pH electrode. 比較電極であることを特徴とする請求項１２の電気化学センサ。   The electrochemical sensor according to claim 12, wherein the electrochemical sensor is a reference electrode. 重量百分率で、ＳｉＯ2 ６０〜７５％、Ｎａ2Ｏ ２〜１４％、Ｌｉ2Ｏ ０〜９％、Ｋ2Ｏ １〜９％（但し、Ｎａ2Ｏ＋Ｌｉ2Ｏ＋Ｋ2Ｏ １０〜２５％）、ＳｒＯ ０〜９％、ＣａＯ １〜９％、ＢａＯ １〜６％、ＭｇＯ ０〜６％、ＺｎＯ ０〜６％（但し、ＳｒＯ＋ＣａＯ＋ＢａＯ＋ＭｇＯ＋ＺｎＯ １０〜２５％）、Ａｌ2Ｏ3 ０〜６％を含有するガラス組成物で形成された電極支持部材と、前記電極支持部材に熔着された白金電極と、を有することを特徴とする電気化学式センサ。 In weight percent, SiO 2 60~75%, Na 2 O 2~14%, Li 2 O 0~9%, K 2 O 1~9% ( however, Na 2 O + Li 2 O + K 2 O 10~25%), Contains SrO 0-9%, CaO 1-9%, BaO 1-6%, MgO 0-6%, ZnO 0-6% (however, SrO + CaO + BaO + MgO + ZnO 10-25%), Al 2 O 3 0-6% An electrochemical sensor, comprising: an electrode support member formed of a glass composition; and a platinum electrode welded to the electrode support member. 電気伝導率セル、ＯＲＰ電極、ポーラログラフ式電極又はガルバニ式電極であることを特徴とする請求項１５の電気化学式センサ。   16. The electrochemical sensor according to claim 15, which is an electric conductivity cell, an ORP electrode, a polarographic electrode, or a galvanic electrode. 前記白金電極には無鉛半田にてリード線が接続され、当該電気化学式センサ外に導かれることを特徴とする請求項１５又は１６の電気化学式センサ。   The electrochemical sensor according to claim 15 or 16, wherein a lead wire is connected to the platinum electrode with lead-free solder, and is led out of the electrochemical sensor. 前記ガラス組成物の熱膨張係数（線膨張係数）は、９．４±２×１０-6／℃であることを特徴とする請求項１０〜１７のいずれかの項に記載の電気化学式センサ。 18. The electrochemical sensor according to claim 10, wherein the glass composition has a thermal expansion coefficient (linear expansion coefficient) of 9.4 ± 2 × 10 −6 / ° C. 18. 前記ガラス組成物の軟化点は、９００℃以下であることを特徴とする請求項１０〜１８のいずれかの項に記載の電気化学式センサ。   The electrochemical sensor according to any one of claims 10 to 18, wherein a softening point of the glass composition is 900 ° C or lower.
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JP2009168637A (en) * 2008-01-16 2009-07-30 Dkk Toa Corp Composite electrode and its manufacturing method
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CN109477811A (en) * 2016-06-16 2019-03-15 哈希公司 Chlorine, oxidation-reduction potential (ORP) and PH measure probe

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