CN1182877A - High-steadiness low-resistance pH electrode sensitive glass - Google Patents

High-steadiness low-resistance pH electrode sensitive glass Download PDF

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Publication number
CN1182877A
CN1182877A CN 96117177 CN96117177A CN1182877A CN 1182877 A CN1182877 A CN 1182877A CN 96117177 CN96117177 CN 96117177 CN 96117177 A CN96117177 A CN 96117177A CN 1182877 A CN1182877 A CN 1182877A
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glass
oxide
resistance
low
agent
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CN 96117177
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Chinese (zh)
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苏渝生
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Institute of Soil Science of CAS
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Institute of Soil Science of CAS
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Abstract

The present invention disctoses a high-stability low-resistance pH electrode sensing glass formed from silicon dioxide, lithia, glass structure regulating agent, glass stability regulating agent and glass resistance regulating agent. The key of said invention lies in that it adopts a specific glass resistance regulating agent vanadium oxide or niobium oxide and mixture made up by mixing them with tantalum according to a proper proportion. The electrode made up by using said invention possesses smaller resistance, higher chemical stability and potential stability, can be used in the fields of clinical medicine, physiological research and low-temp. and non-water system pH detection.

Description

High-steadiness low-resistance pH electrode sensitive glass
The invention belongs to the method test of electricity consumption, galvanochemistry or magnetic or the technical field of analysis of material, relate to a kind of low resistance electrode sensitive glass, particularly a kind of high-steadiness low-resistance pH electrode sensitive glass (G01N27/36).
The performance of pH glass electrode depends primarily on the composition of the sensing glass of making kind electrode.The pH glass electrode that existing various pH electrode sensitive glass is made generally has higher resistance, and (as to make diameter be 8～9mm, wall thickness is the spherical pH electrode of 0.1～0.2mm, internal resistance at room temperature is 50～200M Ω), when making the little pH electrode of microtriche pipe or aciculiform, resistance can reach 10000M Ω or higher.The above-mentioned fact exists:
①Y.S.Su，1993，＂Glass?electrode＂，in《Electorchemical?Methords?inSoll?and?Water》(Ed.by?T.R.Yu?and?G.L.Ji)，Pergamon?Press，Oxford.
②A.V.Gnetov，U.P.Kachalov?and?A.D.Nosdarachev，1986，Glass?Micro-electorde.(R.)＂Nauka＂?Leningrad.
3. R.C.Thomas, 1978.Ion-sensltive Intacellular Microelectrodes, Academic Press, London. in these three pieces of documents detailed description is arranged, when therefore making microelectrode with existing pH sensing glass, or measurement result is very unstable when making conventional electrodes and being used for low-temperature test, and error is very big.For addressing this problem, groundwork concentrates on two aspects for many years: the one, the input impedance that improves surveying instrument, but present stage instrument input impedance can only this to 10 13Ω, and can not long term maintenance; The 2nd, adjust the composition of sensing glass, normally reduce the content of silicon dioxide, increase the content of alkali metal oxide, but this measure descends the chemical stability of glass significantly.Another kind of measure is to add some radioelement oxide (as U 3O 8Or ThO 2), but this measure meeting makes electrode have radioactivity and is not suitable for medical science and physiology.There is minority to add Ta merely 2O 5Though electrode glass can reduce resistance, potential stability, chemical stability are relatively poor, poor processability on flame is not suitable for and is processed into medical microelectrode.
The object of the present invention is to provide a kind of high-steadiness low-resistance pH electrode sensitive glass, to overcome existing above-mentioned defective and deficiency in the prior art.
The present invention realizes in the following manner: a kind of high-steadiness low-resistance pH electrode sensitive glass, and by silicon dioxide (SiO 2), Lithia (Li 2O), glass structure is adjusted agent, glass resistor adjusts agent and stability, glass is adjusted the agent composition, it is strontium oxide strontia (SrO), baryta (BaO) or calcium oxide (CaO) that the fast glass structure of institute is adjusted agent, also can be the potpourri of strontium oxide strontia (SrO) and baryta (BaO), the potpourri of strontium oxide strontia (SrO) and calcium oxide (CaO), the potpourri of baryta (BaO) and calcium oxide (CaO), or above-mentioned these three kinds of hopcalites, it is praseodymium oxide (Pr that above-mentioned stability, glass is adjusted agent 2O 3), cerium oxide (CeO) or lanthana (La 2O 3), also can be praseodymium oxide (Pr 2O 3) and the potpourri of cerium oxide (CeO), praseodymium oxide (Pr 2O 3) and lanthana (La 2O 3) potpourri, cerium oxide (CeO) and lanthana (La 2O 3), or above-mentioned these three kinds of hopcalites, its key is that above-mentioned glass resistor adjustment agent is vanadium pentoxide (V 2O 5) or niobium pentaoxide (Nb 2O 5), also can be vanadium pentoxide (V 2O 5) and niobium pentaoxide (Nb 2O 5) potpourri.
In order to obtain the pH electrode sensitive glass of different resistances, in above-mentioned glass resistor adjustment agent, can also add tantalum pentoxide (Ta again 2O 5), so that satisfy various needs.
Above-mentioned each grammol percentage composition that form to divide is preferably: silicon dioxide (SiO 2) be 62～71%, Lithia (LiO 2) be 20～31%, it is 1～4% that glass structure is adjusted agent, and it is 1～5% that glass resistor is adjusted agent, and it is 1～5% that stability, glass is adjusted agent.
Below by embodiment the present invention is described in further detail, institute's target numerical value all refers to the grammol percentage composition that each composition divides among each embodiment.
[embodiment 1]
A, silicon dioxide (SiO 2) 62.0
B, Lithia (Li 2O) 31.0
C1, strontium oxide strontia (SrO) 2.0
C2, baryta (BaO) 0
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 1.5
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0.5
E2, niobium pentaoxide (Nb 2O 5) 3.0
E3, tantalum pentoxide (Ta 2O 5) 0[embodiment 2]
A, silicon dioxide (SiO 2) 62.5
B, Lithia (Li 2O) 34.5
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 2.0
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 0
D2, cerium oxide (CeO) 2.0
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Nb 2O 5) 3.0
E3, tantalum pentoxide (Ta 2O 5) 0[embodiment 3]
A, silicon dioxide (SiO 2) 62.5
B, Lithia (Li 2O) 30.5
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 0
C3, calcium oxide (CaO) 2.0
D1, praseodymium oxide (Pr 2O 3) 1.5
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0.5
E1, vanadium pentoxide (V 2O 5) 1.0
E2, niobium pentaoxide (Nb 2O 5) 2.0
E3, tantalum pentoxide (Ta 2O 5) 0[embodiment 4]
A, silicon dioxide (SiO 2) 63.0
B, Lithia (Li 2O) 30.5
C1, strontium oxide strontia (SrO) 2.0
C2, baryta (BaO) 0
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 0.5
D2, cerium oxide (CeO) 0.5
D3, lanthana (La 2O 3) 0.5
E1, vanadium pentoxide (V 2O 5) 1.0
E2, niobium pentaoxide (Nb 2O 5) 2.0
E3, tantalum pentoxide (Ta 2O 5) 0[embodiment 5]
A, silicon dioxide (SiO 2) 63.0
B, Lithia (Li 2O) 30.0
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 2.0
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 2.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 1.0
E2, niobium pentaoxide (Nb 2O 5) 0
E3, tantalum pentoxide (Ta 2O 5) 2.0[embodiment 6]
A, silicon dioxide (SiO 2) 63.5
B, Lithia (Li 2O) 29.5
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 1.0
C3, calcium oxide (CaO) 1.0
D1, praseodymium oxide (Pr 2O 3) 1.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Nb 2O 5) 2.0
E3, tantalum pentoxide (Ta 2O 5) 2.0[embodiment 7]
A, silicon dioxide (SiO 2) 64.0
B, Lithia (Li 2O) 28.0
C1, strontium oxide strontia (SrO) 2.0
C2, baryta (BaO) 0.5
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 2.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0.5
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Bb 2O 5) 2.0
E3, tantalum pentoxide (Ta 2O 5) 1.0[embodiment 8]
A, silicon dioxide (SiO 2) 64.0
B, Lithia (Li 2O) 28.5
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 1.8
C3, calcium oxide (CaO) 0.7
D1, praseodymium oxide (Pr 2O 3) 1.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 1.0
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Nb 2O 5) 1.0
E3, tantalum pentoxide (Ta 2O 5) 2.0[embodiment 9]
A, silicon dioxide (SiO 2) 64.0
B, Lithia (Li 2O) 28.0
C1, strontium oxide strontia (SrO) 1.5
C2, baryta (BaO) 1.0
C3, calcium oxide (CaO) 0.5
D1, praseodymium oxide (Pr 2O 3) 2.5
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0.5
E1, vanadium pentoxide (V 2O 5) 0.5
E2, niobium pentaoxide (Nb 2O 5) 0.5
E3, tantalum pentoxide (Ta 2O 5) 1.0[embodiment 10]
A, silicon dioxide (SiO 2) 64.0
B, Lithia (Li 2O) 28.0
C1, strontium oxide strontia (SrO) 1.0
C2, baryta (BaO) 0
C3, calcium oxide (CaO) 2.0
D1, praseodymium oxide (Pr 2O 3) 2.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0.4
E2, niobium pentaoxide (Nb 2O 5) 2.0
E3, tantalum pentoxide (Ta 2O 5) 0.6[embodiment 11]
A, silicon dioxide (SiO 2) 64.5
B, Lithia (Li 2O) 28.0
C1, strontium oxide strontia (SrO) 1.0
C2, baryta (BaO) 1.0
C3, calcium oxide (CaO) 0.5
D1, praseodymium oxide (Pr 2O 3) 2.0
D2, cerium oxide (CeO) 0.5
D3, lanthana (L 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Nb 2O 5) 1.0
E3, tantalum pentoxide (Ta 2O 5) 1.5[embodiment 12]
A, silicon dioxide (SiO 2) 64.5
B, Lithia (Li 2O) 27.0
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 1.0
C3, calcium oxide (CaO) 1.0
D1, praseodymium oxide (Pr 2O 3) 1.0
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 1.0
E1, vanadium pentoxide (V 2O 5) 1.0
E2, niobium pentaoxide (Nb 2O 5) 3.5
E3, tantalum pentoxide (Ta 2O 5) 0[embodiment 13]
A, silicon dioxide (SiO 2) 65.0
B, Lithia (Li 2O) 26.6
C1, strontium oxide strontia (SrO) 1.0
C2, baryta (BaO) 0.5
C3, calcium oxide (CaO) 0.4
D1, praseodymium oxide (Pr 2O 3) 1.5
D2, cerium oxide (CeO) 0
D3, lanthana (La 2O 3) 1.0
E1, vanadium pentoxide (V 2O 5) 1.0
E2, niobium pentaoxide (Nb 2O 5) 3.0
E3, tantalum pentoxide (Ta 2O 5) 0
[embodiment 14]
A, silicon dioxide (SiO 2) 67.0
B, Lithia (Li 2O) 26.0
C1, strontium oxide strontia (SrO) 0
C2, baryta (BaO) 0.5
C3, calcium oxide (CaO) 0
D1, praseodymium oxide (Pr 2O 3) 3.0
D2, cerium oxide (CeO) 0.5
D3, lanthana (La 2O 3) 0
E1, vanadium pentoxide (V 2O 5) 0
E2, niobium pentaoxide (Nb 2O 5) 1.6
E3, tantalum pentoxide (Ta 2O 5) 1.4
The concrete production technology of high-steadiness low-resistance pH electrode sensitive glass of the present invention can be carried out as follows:
One, the prescription by high-steadiness low-resistance pH electrode sensitive glass of the present invention is ready to various oxides or salt (C.P. level or A.R. level) corresponding, can resolve into oxide under heating condition, and drying is 2～4 hours under 105～120 ℃ of conditions;
Two, above-mentioned raw materials is ground with agate mortar, cross 60 mesh sieves, under 105～120 ℃ of conditions dry 1 hour once more;
Three, press the foregoing description and decide the proportioning weighing,, in the agate mortar ground and mixed, obtain powder then each raw material blending;
Four, powder is put into platinum alloy crucible, melt refining in the Elema electric furnace, melt the refining temperature in three stages: the phase one feeds intake about 950～1000 ℃, powder is melted be smelt vitreum; Subordinate phase stirs 1 time 1150～1200 ℃ of meltings 4 hours; Phase III is removed bubble in the vitreum 1200 ℃ of meltings;
Five, be drawn into the sensing glass rod of certain diameter.
Utilize above-mentioned sensing glass bar material to cooperate corresponding pole glass just can produce required high-steadiness low-resistance pH glass electrode according to different needs.
The high-steadiness low-resistance pH glass electrode that the high-steadiness low-resistance pH electrode sensitive glass that utilizes the present invention to obtain manufactures is littler 5～10 times than the electrode internal resistance made from general sensing glass, higher chemical stability and potential stability are arranged, owing to do not use and contain radioactive element oxide, can be used for the manufacturing of little pH electrode that clinical medicine and physiological Study use, be applicable to the various low-resistance pH electrode fields that particularly pH measures in low temperature and the non-aqueous system that need simultaneously.

Claims (3)

1, a kind of high-steadiness low-resistance pH electrode sensitive glass, by
A, silicon dioxide (SiO 2),
B, Lithia (Li 2O),
C, glass structure are adjusted agent,
D, stability, glass adjust agent and
E, glass resistor are adjusted agent and are formed a kind of or any several hopcalite of described glass structure adjustment manufacturing in following oxide:
C1, strontium oxide strontia (SrO),
C2, calcium oxide (CaO),
C3, baryta (BaO), fast stability, glass adjust agent and be selected from a kind of or any several hopcalite in the following oxide:
D1, praseodymium oxide (Pr 2O 3),
D2, cerium oxide (CeO),
D3, lanthana (La 2O 3), it is characterized in that described glass resistor adjustment agent is selected from a kind of or its potpourri in the following oxide:
E1, vanadium pentoxide (V 2O 5),
E2, niobium pentaoxide (Nb 2O 5).
2,, it is characterized in that also containing in the above-mentioned glass resistor adjustment agent according to the high-steadiness low-resistance pH electrode sensitive glass of claim 1 regulation:
E3, tantalum pentoxide (Ta 2O 5).
3,, it is characterized in that the grammol percentage composition that described each composition divides is according to the high-steadiness low-resistance pH electrode sensitive glass of claim 1 or 2 regulations:
A, silicon dioxide (SiO 2) 62～71%,
B, Lithia (Li 2O) 20～31%,
C, glass structure are adjusted agent 0.5～4%,
D, stability, glass are adjusted agent 1～5%,
E, glass resistor are adjusted agent 1～5%.
CN 96117177 1996-11-20 1996-11-20 High-steadiness low-resistance pH electrode sensitive glass Pending CN1182877A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 96117177 CN1182877A (en) 1996-11-20 1996-11-20 High-steadiness low-resistance pH electrode sensitive glass

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Application Number Priority Date Filing Date Title
CN 96117177 CN1182877A (en) 1996-11-20 1996-11-20 High-steadiness low-resistance pH electrode sensitive glass

Publications (1)

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CN1182877A true CN1182877A (en) 1998-05-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100224490A1 (en) * 2007-10-19 2010-09-09 Hach Company Multiple-electrode ionic probe

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100224490A1 (en) * 2007-10-19 2010-09-09 Hach Company Multiple-electrode ionic probe
US8608925B2 (en) * 2007-10-19 2013-12-17 Hach Company Multiple-electrode ionic probe
CN101828107B (en) * 2007-10-19 2014-07-23 哈赫公司 Multiple-electrode ionic probe
CN104122313A (en) * 2007-10-19 2014-10-29 哈赫公司 Multiple-electrode ionic probe
CN104122313B (en) * 2007-10-19 2017-08-22 哈赫公司 multiple-electrode ionic probe

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