CN109507253A - Yttrium oxide combination electrode and preparation method thereof and the pH sensor for using the electrode - Google Patents
Yttrium oxide combination electrode and preparation method thereof and the pH sensor for using the electrode Download PDFInfo
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- CN109507253A CN109507253A CN201811365735.9A CN201811365735A CN109507253A CN 109507253 A CN109507253 A CN 109507253A CN 201811365735 A CN201811365735 A CN 201811365735A CN 109507253 A CN109507253 A CN 109507253A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The present invention provides a kind of yttrium oxide combination electrodes, and including iridium wire and the iridium oxide layer for being formed in the iridium wire surface, the iridium oxide layer is made of 60%~65% iridium dioxide and 35%~40% iridous oxide.The present invention also provides a kind of preparation methods of above-mentioned yttrium oxide combination electrode, including pre-treatment, activation processing, sintering processes and water cooling treatment and etc., the step of activation processing includes first being activated with iridium wire of the dilute hydrochloric acid to the cleaning, then carry out the iridium wire that washing and drying treatment is activated；The step of sintering processes includes the iridium wire that the activation is first impregnated with sodium hydroxide solution, then carries out high temperature sintering and handle to obtain sintered iridium wire.The present invention also provides a kind of pH sensors using above-mentioned yttrium oxide combination electrode.Above-mentioned yttrium oxide combination electrode has preferable consistency and stability, so that above-mentioned pH sensor has preferable stability and sensitivity, and preparation method is simple, and cost is relatively low.
Description
Technical field
The invention belongs to sensor field more particularly to a kind of yttrium oxide combination electrode and preparation method thereof and use the electricity
The pH sensor of pole.
Background technique
PH value is to measure an important indicator of water standard, many natural phenomena, chemistry and lifes for designing aqueous solution
Production process, in addition including we daily life it is all related to pH value, therefore, in industry, agricultural, medicine, environmental protection, scientific research, the people
With etc. all various aspects require detection water quality pH value.The most commonly used pH electrode of pH sensor is pH vitreous electricity at present
Pole, since glass electrode is there are some defects, the problems such as cannot being used under such as frangible, high temperature, and all-solid-state pH sensor core
Center portion part is metal oxide, has the condition used at high temperature, and high mechanical strength, is easy to make and be miniaturized etc. special
Point can make up the defect of pH glass electrode.Therefore, in recent years, metal oxide pH electrode especially iridium/iridium oxide electrode
Preparation and application are concerned.
Iridium/iridium oxide electrode mainly has electrochemistry cyclic voltammetric, electro-deposition, sputtering, high temperature carbonate to aoxidize 4 kinds of systems at present
Preparation Method.John E Baur and Thomas W Spaine is in an entitled " Electro-chemical deposition
Of iridium (IV) oxide from alkaline solutions of iridium (III) oxide [J] ", hair
In J Electro Analyt Chem, 1988,443:208 opinion is disclosed herein to be prepared table with electrochemical cyclic voltammetry
Iridium/iridium oxide electrode, but iridium/iridium oxide electrode reproducibility of this method preparation is poor, and the electrode of preparation can not show to fix
PH- potential response performance.Lin Changjian etc. is in an entitled " Fabrication of IrO2-pH microelectrode
and its application study of chemical micro-environment at steel/concrete
Interface [J] " is published in Corros Sci Protect Techn, 2002,14 (5): fortune is disclosed herein in 305 opinion
Iridium/iridium oxide electrode is prepared with Anodic sedimentation, but its electroplating bath components is more complex and preparation process is not easy to control.It splashes
Penetrate method preparation iridium/iridium oxide electrode its can this spy's response close to theoretical value, but electrode potential drift about larger and sputtering equipment compared with
It is expensive.
Therefore, the problems such as that there are reproducibility is poor for existing iridium/iridium oxide electrode, and preparation process is more complex, higher cost,
To limit the application using iridium/iridium oxide electrode pH sensor.
Summary of the invention
In view of this, it is necessory to provide a kind of yttrium oxide combination electrode and preparation method thereof and passed using the pH of the electrode
Sensor, to solve the above problems.
The present invention provides a kind of yttrium oxide combination electrode, including iridium wire and the iridium oxide layer for being formed in the iridium wire surface,
Wherein, by mass percentage, the iridium oxide layer is by 60%~65% iridium dioxide and 35%~40% iridous oxide group
At.
The present invention also provides a kind of preparation methods of above-mentioned yttrium oxide combination electrode, comprising the following steps:
Pre-treatment successively polishes to iridium wire, polished, cleaning treatment, obtains clean iridium wire；
Activation processing is first activated with iridium wire of the dilute hydrochloric acid to the cleaning, then carries out washing and drying treatment, is obtained
The iridium wire of activation；
Sintering processes first impregnate the iridium wire of the activation with sodium hydroxide solution, then carry out high temperature sintering processing, after obtaining sintering
Iridium wire；
The water cooling treatment cooling sintered iridium wire of water cooling, obtains the yttrium oxide combination electrode.
Based on above-mentioned, the step of activation processing includes: first to activate the cleaning with the dilute hydrochloric acid of 0.01~1 mol/L
5~15min of iridium wire, then cleaned be cleaned by ultrasonic with deionized water and ethyl alcohol respectively, dried, obtain the iridium of the activation
Silk.
Based on above-mentioned, the step of sintering processes includes: with the NaOH solution of 1.5~4.5 mol/L by the activation
Iridium wire impregnate 30~40 h, keep the temperature 1.5~3 hours in 700 DEG C~780 DEG C environment, obtain the sintered iridium wire.
Based on above-mentioned, the step of pre-treatment include: first by the iridium wire successively use 400#, 800#, 1200#,
1500#, 2000# sand paper are polished, the iridium wire after being polished；Iridium wire after the polishing is processed by shot blasting, is obtained
Iridium wire after polishing；The iridium wire after the polishing is cleaned by ultrasonic with deionized water and ethyl alcohol respectively, obtains the cleaning
Iridium wire.
It include being beaten using chamois leather described based on the step of above-mentioned, the iridium wire to after the polishing is processed by shot blasting
Iridium wire after mill is processed by shot blasting.
The present invention also provides a kind of pH sensors using above-mentioned yttrium oxide combination electrode, wherein the yttrium oxide is compound
Electrode is used as response electrode.
Based on above-mentioned, the pH sensor further includes shell, and the yttrium oxide compound electric is fixed on the top surface of the shell
Pole and reference electrode, the oxide combination electrode and the reference electrode interval are arranged, and the shell is porous engraved structure.
Based on above-mentioned, the pH sensor further includes the circuit board that the top surface of the shell is arranged in, circuit board difference
It is connect with the oxide combination electrode, the reference electrode.Preferably, the circuit board is internal circuit board.
Based on above-mentioned, the pH sensor further includes two suture introducing needles for being mounted on the circuit board upper surface, wherein one
A suture introducing needle is connect by the circuit board with the oxide combination electrode, another suture introducing needle passes through the circuit board
It is connect with the reference electrode.
Based on above-mentioned, the pH sensor further includes the cover board that the circuit board upper surface is arranged in, and two suture introducing needles are inserted
In the cover board.
Compared with prior art, yttrium oxide combination electrode provided by the invention includes iridium wire and the iridium oxide layer, and is somebody's turn to do
Iridium oxide layer is made of 60%~65% iridium dioxide and 35%~40% iridous oxide, and by successively carrying out to iridium wire
Prepared by pre-treatment, activation processing, sintering processes and water cooling treatment, and high temperature burning is first carried out using NaOH solution immersion again
Knot processing, so that the yttrium oxide combination electrode has relatively good consistency, stability and sensitivity.And it is molten by NaOH
Liquid carries out high temperature sintering processing after impregnating again, can reduce sintering temperature, achievees the purpose that reduce energy consumption.
It in the preparation process of yttrium oxide combination electrode provided by the invention, is activated using dilute hydrochloric acid, so that institute
The iridium wire for stating activation has certain surface-active, uses NaOH solution can be fine during being sintered subsequent
Ground is in conjunction with oxygen, so that the surface-active of sintered iridium wire is more preferable, to improve the yttrium oxide combination electrode prepared
Stability and sensitivity.
Further, it is avoided using 5~15min of iridium wire that the dilute hydrochloric acid of 0.01~1 mol/L activates the cleaning because of hydrochloric acid
Concentration is too low or activation time is short, does not have the effect of activation, also avoids because concentration of hydrochloric acid is excessively high or the too long appearance of activation time
The case where iridium wire overactivity even corrodes, to guarantee that iridium wire is adequately activated, it is ensured that improve the oxygen prepared
Change the stability and sensitivity of iridium combination electrode.
In the preparation method of yttrium oxide combination electrode provided by the invention, using chamois leather to polishing in pretreatment process
The characteristics of iridium wire afterwards is processed by shot blasting, is based on chamois leather itself, so that iridium wire after polishing is in mirror surface, surface roughness is big
It is big to reduce, be conducive to the stability and sensitivity that improve yttrium oxide combination electrode, and then be conducive to improve multiple using the oxide
The stability and sensitivity of the pH sensor of composite electrode.
PH sensor provided by the invention using above-mentioned yttrium oxide combination electrode not only have relatively good stability and
Sensitivity, signal also are compliant with Nernst equation, equation linear rule, and good mechanical property, and volume is smaller, and preparation is simple, make
With conveniently.
Further, pH sensor provided by the invention includes the shell with porous engraved structure, is guaranteeing pH sensor
On the basis of normal work, moreover it is possible to which adequately protection is located at the oxide combination electrode and reference electrode of the enclosure interior, avoids
Or prevent electrode in storage or use process by the destruction of foreign matter, but also can be reduced or avoid during storage by
The pollution of external environment is conducive to the reproducibility, consistency, service life and the accuracy that improve the pH sensor, is conducive to expand
The applicable situation of big pH sensor.
Further, pH sensor provided by the invention includes circuit board, especially internal circuit board, can be with telegraph circuit
More diversification is converted, multiple occasions are suitable for, interface is more convenient.
Detailed description of the invention
Fig. 1 is the cross-sectional view of the structure for the yttrium oxide combination electrode that the embodiment of the present invention 1 provides.
Fig. 2 is that the structure for the pH sensor using yttrium oxide combination electrode shown in FIG. 1 that the embodiment of the present invention 1 provides is shown
It is intended to.
Fig. 3 is pH- potential response curve graph measured by the pH sensor of the offer of the embodiment of the present invention 2.
Fig. 4 is the response stability contrast curve chart being activated to yttrium oxide combination electrode provided by the invention.
Fig. 5 is the response sensitivity contrast curve chart being activated to yttrium oxide combination electrode provided by the invention.
Fig. 6 is response stability contrast curve chart of the sintering processes to yttrium oxide combination electrode provided by the invention.
Fig. 7 is response consistency contrast curve chart of the sintering processes to yttrium oxide combination electrode provided by the invention.
Wherein, the numbers in each figure: 1 yttrium oxide combination electrode, 2 iridium wires, 3 iridium oxide layers, 4 shells, 5
Reference electrode, 6 internal circuit boards, 7 two suture introducing needles, 8 cover boards, 41 top surfaces, 42 bottom surfaces, 43 sides, 44 through-holes.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be described in further detail.
Embodiment 1
It please participate in Fig. 1, the embodiment of the present invention 1 provides a kind of yttrium oxide combination electrode 1, including iridium wire 2 and is formed in the iridium wire
The iridium oxide layer 3 on surface, wherein by mass percentage, the iridium oxide layer 3 is by 60% iridium dioxide and 40% three oxidations
Two iridium composition.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned yttrium oxide combination electrode, comprising the following steps:
Pre-treatment first successively polishes iridium wire with 400#, 800#, 1200#, 1500#, 2000# sand paper, after being polished
Iridium wire；The iridium wire after the polishing is processed by shot blasting using chamois leather, the iridium wire after being polished；With deionized water and ethyl alcohol
Iridium wire after the polishing is alternately cleaned by ultrasonic, is cleaned by ultrasonic 10 min every time, cleans three circulations, obtain described clean
Net iridium wire；The dust mainly cleaned and generated during grinding and buffing is cleaned with deionized water in the step, uses ethyl alcohol
Cleaning mainly avoids organic substance from being adsorbed on iridium wire surface in deionized water cleaning process.
Be activated and first activate 15 min of iridium wire of the cleaning with the dilute hydrochloric acid of 0.05 mol/L, then successively spend from
Sub- water and ethyl alcohol are respectively cleaned by ultrasonic 5 min, then clean 15 min of ultrasonic cleaning with deionized water again, dry, and obtain described
The iridium wire of activation；First cleaned with deionized water in the step is to be primarily due to be to take out first use deionization inside hydrochloric acid
Water washes its surface institute band acid solution, avoids hurting people, is next cleaned again with ethyl alcohol and mainly organic substance is avoided to wash acid
During be adsorbed on iridium wire surface, washed with water again after ethyl alcohol cleaning, be attached to iridium wire surface primarily to washing away
Ethyl alcohol.
The iridium wire of the activation is impregnated 40 h with the NaOH solution of 1.5 mol/L by sintering processes, in 780 DEG C of environment
Heat preservation 1.5 hours, obtains the sintered iridium wire；
The water cooling treatment cooling sintered iridium wire of water cooling, obtains above-mentioned yttrium oxide combination electrode.
Fig. 2 please be participate in, the embodiment of the present invention also provides a kind of pH sensor using above-mentioned yttrium oxide combination electrode, including
Shell 4, the yttrium oxide combination electrode 1, reference electrode 5,6, two suture introducing needles 7 of internal circuit board and cover board 8.Wherein, described
Shell 4 is porous engraved structure, is the cavity body structure surrounded by top surface 41, bottom surface 42 and side 43.The interior table of the top surface 41
The yttrium oxide combination electrode 1 and the reference electrode 5 are mounted side by side on face.The yttrium oxide combination electrode 1 and the reference
The setting of the interval of electrode 5.The reference electrode 5 can be calomel electrode or Ag/AgCl electrode, reference electrode described in the present embodiment
5 be Ag/AgCl electrode.The internal circuit board 6 is installed on the outer surface of the top surface 41.The internal circuit board 6 it is another
Side is equipped with the cover board 8, and the internal circuit board 6 is clamped between cover board 8 and the shell 4.The cover board 8 is by electric exhausted
Edge is made, such as epoxy resin.Two suture introducing needles 7 intervals, which are arranged, is simultaneously inserted into the cover board 8, and by the cover board 8 with
The internal circuit board 6 connects.The yttrium oxide combination electrode 1 and the reference electrode 5 pass through the internal circuit board 6 and two
A suture introducing needle 7 is electrically connected, one of them described suture introducing needle 7 passes through the internal circuit board 6 and the oxide compound electric
Pole 1 is electrically connected, another suture introducing needle 7 is electrically connected by the internal circuit board 6 with the reference electrode 5.
The inner cavity of the shell 4 is for holding prepare liquid.Specifically, the top surface 41 is plate, without through-hole；It is described
Multiple through-holes 44 are all distributed on bottom surface 42 and the side 43, the diameter of the through-hole 44 on the side 43 is greater than the bottom surface
The diameter of through-hole 44 on 42；Prepare liquid enters the inner cavity of the shell 4 by the through-hole 44 on the bottom surface 42 and side 43,
It comes into full contact with the yttrium oxide combination electrode 1 and reference electrode 5 as electrolyte；The yttrium oxide combination electrode 1 is with making a sound
Electrode is answered, constitutes primary battery together with reference electrode 5 and prepare liquid, makes the pH normal operation of sensor.The all-solid-state pH
Sensor further includes the peripheral protective cover of cover on the housing, to be reduced or avoided during storage by external environment
Pollution, is conducive to the reproducibility, consistency and the accuracy that improve the all-solid-state pH sensor.
Embodiment 2
The embodiment of the present invention 2 provide a kind of yttrium oxide combination electrode, the yttrium oxide combination electrode that structure and embodiment 1 provide
Structure it is essentially identical, the difference is that: by mass percentage, the iridium oxide layer by 63.8% iridium dioxide and
36.2% iridous oxide composition.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned yttrium oxide combination electrode, comprising the following steps:
Pre-treatment first successively polishes iridium wire with 400#, 800#, 1200#, 1500#, 2000# sand paper, after being polished
Iridium wire；The iridium wire after the polishing is processed by shot blasting using chamois leather, the iridium wire after being polished；With deionized water and ethyl alcohol
Iridium wire after the polishing is alternately cleaned by ultrasonic, is cleaned by ultrasonic 15 min every time, cleans three circulations, obtain described clean
Net iridium wire；
Be activated and first activate 10 min of iridium wire of cleaning with the dilute hydrochloric acid of 0.5 mol/L, then successively use deionized water with
Ethyl alcohol is respectively cleaned by ultrasonic 10 min, then cleans 10 min of ultrasonic cleaning with deionized water again, dries, obtain the activation
Iridium wire；
The iridium wire of the activation is impregnated 35 h with the NaOH solution of 3 mol/L by sintering processes, keeps the temperature 2 in 750 DEG C of environment
H obtains the sintered iridium wire；
The water cooling treatment cooling sintered iridium wire of water cooling, obtains above-mentioned yttrium oxide combination electrode.
The present embodiment also provides a kind of pH sensor, the basic phase of structure for the pH sensor that structure is provided with embodiment 1
Together, the difference is that: being used as response electrode in pH sensor provided in this embodiment is yttrium oxide provided in this embodiment
Combination electrode.
PH sensor provided in an embodiment of the present invention is used to measure pH value respectively as 4.01,6.86 and 9.18 buffer solution
Voltage, and draw the curve of pH value and voltage, as shown in Figure 3.As can be seen from Figure 3: the voltage of pH value and pH sensor
It substantially changes linearly, to illustrate that the electric signal of the pH sensor meets Nernst equation, journey linear rule.
Embodiment 3
The embodiment of the present invention 3 provide a kind of yttrium oxide combination electrode, the yttrium oxide combination electrode that structure and embodiment 1 provide
Structure it is essentially identical, the difference is that: by mass percentage, the iridium oxide layer is by 65% iridium dioxide and 35%
Iridous oxide composition.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned yttrium oxide combination electrode, comprising the following steps:
Pre-treatment first successively polishes iridium wire with 400#, 800#, 1200#, 1500#, 2000# sand paper, after being polished
Iridium wire；The iridium wire after the polishing is processed by shot blasting using chamois leather, the iridium wire after being polished；With deionized water and ethyl alcohol
Iridium wire after the polishing is alternately cleaned by ultrasonic, is cleaned by ultrasonic 5 min every time, cleans three circulations, obtain described clean
Net iridium wire；
It is activated 5 min of iridium wire for first activating the cleaning with the dilute hydrochloric acid of 1 mol/L, then successively uses deionized water and second
Alcohol is respectively cleaned by ultrasonic 5 min, then cleans 3 min of ultrasonic cleaning with deionized water again, dries, obtain the iridium of the activation
Silk；
The iridium wire of the activation is impregnated 30 h with the NaOH solution of 4.5 mol/L by sintering processes, keeps the temperature 3 in 700 DEG C of environment
H obtains the sintered iridium wire；
The water cooling treatment cooling sintered iridium wire of water cooling, obtains above-mentioned yttrium oxide combination electrode.
The present embodiment also provides a kind of pH sensor, the basic phase of structure for the pH sensor that structure is provided with embodiment 1
Together, the difference is that: being used as response electrode in pH sensor provided in this embodiment is yttrium oxide provided in this embodiment
Combination electrode.
Performance test
As can be seen from the above: activation processing in the stability of yttrium oxide combination electrode and sensitivity and its preparation process and
Sintering processes step has important influence.Below by taking the oxide combination electrode that the embodiment of the present invention 2 provides as an example, further solve
Release the performance of oxide combination electrode provided by the invention.
1, the influence being activated
Subjects: sample sets are by being activated the yttrium oxide combination electrode formed and bareing Ag/AgCl electrode composition
Sensor, wherein the yttrium oxide combination electrode is the method system that the iridium wire of 15 cm diameter, 1 mm is provided according to embodiment 2
For what is gone out；
The sensor that contrast groups are formed without the yttrium oxide combination electrode formed and bareing Ag/AgCl electrode is activated,
Wherein, without the yttrium oxide combination electrode in the preparation method and sample group for being activated the yttrium oxide combination electrode formed
Preparation method is essentially identical, the difference is that the yttrium oxide combination electrode of contrast groups preparation does not pass through hydrochloric acid activation processing.
Electrode response stability conditions: the buffering for being respectively 4.01 in pH value by the sensor of sample sets and contrast groups
The determination sensor response time is 0,2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 in solution
Electricity when min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min
Pressure, to reflect influence of the activity processing to electrode response stability.Wherein, measurement result is as shown in Figure 4.
Electrode response sensitivity test condition: by the sensor of sample sets and contrast groups respectively pH value be 4.01,6.86,
Measurement response voltage in 9.18 buffer solution, to reflect influence of the activity processing to electrode response sensitivity.Wherein, measurement knot
Fruit is as shown in Figure 5.
As can be seen from Figure 4: within the response time of 120 min, contrast groups are formed without hydrochloric acid activation processing
The response voltage of yttrium oxide combination electrode fluctuates between 186 mV and 139 mV, and fluctuating range is bigger, so, contrast groups
The stability of yttrium oxide combination electrode is poor；And the sound of the yttrium oxide combination electrode of formation of the sample sets by hydrochloric acid activation processing
Answer voltage to fluctuate between 160 mV and 151 mV, fluctuating range is smaller, so, the yttrium oxide combination electrode of sample sets it is steady
It is qualitative relatively good；Further illustrate iridium wire by hydrochloric acid activation processing can be improved preparation from yttrium oxide combination electrode response
Stability.
As can be seen from Figure 5: though the variation of the voltage of sample sets and contrast groups energy pH value changes linearly, sample
PH value-voltage straight line slope that product group is formed is significantly greater than pH value-voltage straight line slope of contrast groups formation, therefore, sample
The sensitivity of the yttrium oxide combination electrode of product group is relatively high, thus illustrate iridium wire by hydrochloric acid activation processing can be improved preparation from
Yttrium oxide combination electrode response sensitivity.
2, the influence of sintering processes
Subjects: what the yttrium oxide combination electrode and bareing Ag/AgCl electrode that sample sets are formed by NaOH processing formed
Sensor, wherein the yttrium oxide combination electrode is the method system that the iridium wire of 15 cm diameter, 1 mm is provided according to embodiment 2
For what is gone out；
Contrast groups pass through Na2CO3The yttrium oxide combination electrode and bareing Ag/AgCl electrode that powder sintered processing is formed form
Sensor, wherein Na2CO3Oxidation in the preparation method and sample group of the yttrium oxide combination electrode that powder sintered processing is formed
The preparation method of iridium combination electrode is essentially identical, the difference is that: the yttrium oxide combination electrode of contrast groups preparation is to pass through
After the clean iridium wire that pre-treatment obtains, by clean iridium wire Na2CO3Powder covers and in 850 DEG C of sintering processes.
Electrode response stability conditions: the buffering for being respectively 4.01 in pH value by the sensor of sample sets and contrast groups
The determination sensor response time is 0,2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 in solution
Electricity when min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min
Pressure, to reflect influence of the activity processing to electrode response stability.Wherein, measurement result is as shown in Figure 6.
Electrode response Consistency test condition: 11 sample sets and 11 contrast groups are provided, by these sample sets and comparison
The sensor of group measures response voltage in the buffer solution of pH value 4.01, takes in 10 min in the buffer solution of pH value 4.01
Response voltage value of the voltage change less than 10 mV.Wherein, measurement result is as shown in Figure 7.
As can be seen from Figure 6: within the response time of 120 min, contrast groups use Na2CO3The oxygen that sintering processes are formed
The response voltage for changing iridium combination electrode fluctuates between 329 mV and 83 mV, and fluctuating range is bigger, so, the oxygen of contrast groups
The stability for changing iridium combination electrode is poor；And the response voltage of the yttrium oxide combination electrode of sample sets 160 mV and 151 mV it
Between fluctuate, fluctuating range is smaller, so, the stability of the yttrium oxide combination electrode of sample sets is relatively good；Therefore, by NaOH
Solution is sintered the yttrium oxide combination electrode to be formed again response stability after impregnating is much higher than through Na2CO3Sintering processes
The response stability of the yttrium oxide combination electrode of formation.
As can be seen from Figure 7: response voltage of 11 contrast groups in the buffer solution of pH value 4.01 321 mV with-
It is fluctuated between 60 mV, fluctuating range is bigger, illustrates contrast groups through Na2CO3The yttrium oxide combination electrode that sintering processes are formed
Reproducibility is poor, and comparison of coherence is poor；Response voltage of 11 sample sets in the buffer solution of pH value 4.01 153 mV with
It is fluctuated between 149 mV, fluctuating range is smaller, and fluctuating range can be ignored relative to its voltage value, to illustrate sample
Group is sintered the reproducible of the yttrium oxide combination electrode to be formed again after NaOH solution is impregnated, and comparison of coherence is good.
Finally it should be noted that: the above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, it should be understood by those ordinary skilled in the art that: still
It can modify to a specific embodiment of the invention or some technical features can be equivalently replaced；Without departing from this hair
The spirit of bright technical solution should all cover within the scope of the technical scheme claimed by the invention.
Claims (10)
1. a kind of yttrium oxide combination electrode, including iridium wire and the iridium oxide layer for being formed in the iridium wire surface, wherein press quality hundred
Score meter, the iridium oxide layer are made of 60%~65% iridium dioxide and 35%~40% iridous oxide.
2. a kind of preparation method of yttrium oxide combination electrode described in claim 1, comprising the following steps:
Pre-treatment successively polishes to iridium wire, polished, cleaning treatment, obtains clean iridium wire；
Activation processing is first activated with iridium wire of the dilute hydrochloric acid to the cleaning, then carries out washing and drying treatment, is obtained
The iridium wire of activation；
Sintering processes first impregnate the iridium wire of the activation with sodium hydroxide solution, then carry out high temperature sintering processing, after obtaining sintering
Iridium wire；
The water cooling treatment cooling sintered iridium wire of water cooling, obtains the yttrium oxide combination electrode.
3. the preparation method of yttrium oxide combination electrode according to claim 2, which is characterized in that the step of the activation processing
Suddenly include: 5~15min of iridium wire of cleaning is first activated with the dilute hydrochloric acid of 0.01~1 mol/L, then respectively use deionized water with
Ethyl alcohol cleaning is cleaned by ultrasonic, and is dried, is obtained the iridium wire of the activation.
4. the preparation method of yttrium oxide combination electrode according to claim 2 or 3, which is characterized in that the sintering processes
The step of include: that the iridium wire of the activation is impregnated into 30~40 h with the NaOH solution of 1.5~4.5 mol/L, 700 DEG C~
1.5~3 hours are kept the temperature in 780 DEG C of environment, obtains the sintered iridium wire.
5. the preparation method of yttrium oxide combination electrode according to claim 4, which is characterized in that the step of the pre-treatment
It include: that first the iridium wire is successively polished with 400#, 800#, 1200#, 1500#, 2000# sand paper, the iridium after being polished
Silk；Iridium wire after the polishing is processed by shot blasting, the iridium wire after being polished；Respectively with deionized water and ethyl alcohol to described
Iridium wire after polishing is cleaned by ultrasonic, and the iridium wire of the cleaning is obtained.
6. the preparation method of yttrium oxide combination electrode according to claim 1, which is characterized in that it is described to the polishing after
Iridium wire the step of being processed by shot blasting include being processed by shot blasting using chamois leather to the iridium wire after the polishing.
7. a kind of pH sensor using yttrium oxide combination electrode described in claim 1, which is characterized in that the yttrium oxide is multiple
Composite electrode is used as response electrode.
8. pH sensor according to claim 7, which is characterized in that further include shell, be fixed on the top surface of the shell
The yttrium oxide combination electrode and reference electrode, the oxide combination electrode and the reference electrode interval are arranged, the shell
Body is porous engraved structure.
9. pH sensor according to claim 8, which is characterized in that further include the circuit that the top surface of the shell is arranged in
Plate, the circuit board are connect with the oxide combination electrode, the reference electrode respectively.
10. pH sensor according to claim 9, which is characterized in that further include that the circuit board upper surface is arranged in
Cover board and two suture introducing needles being inserted in the cover board, two suture introducing needles and the circuit board contacts, and one of them
The suture introducing needle is connect by the circuit board with the oxide combination electrode, another described suture introducing needle passes through the circuit
Plate is connect with the reference electrode.
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