CN1008181B - Improved ion-sensitive electrode - Google Patents
Improved ion-sensitive electrodeInfo
- Publication number
- CN1008181B CN1008181B CN 85107084 CN85107084A CN1008181B CN 1008181 B CN1008181 B CN 1008181B CN 85107084 CN85107084 CN 85107084 CN 85107084 A CN85107084 A CN 85107084A CN 1008181 B CN1008181 B CN 1008181B
- Authority
- CN
- China
- Prior art keywords
- ion
- sensitive
- electrode
- spherical shell
- pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Joining Of Glass To Other Materials (AREA)
- Glass Compositions (AREA)
Abstract
The present invention relates to an improved ion sensitive electrode which is composed of an infrared absorption glass tube (12) and a prefabricated part (30) made of ion sensitive material, wherein infrared can pass through the ion sensitive material, and the diameter of the spherical head (32) of the prefabricated part (30) is obviously larger than the diameter of the tube (12). The spherical head (32) is put at the port of the lip part of the tube (12), and the lip part is irradiated by an infrared source (15); therefore, the lip part is melted to adhere the tube (12) to the head (32). When a melted assembly is cooled, the rest part of the prefabricated part (30) cracks and falls off so as to leave a complete electrode.
Description
This invention is relevant with ion-sensitive electrode, and it is an electrode with flat surface, adopts the radiating method with the end face of a part spherical shell welding made from ion-sensitive film at a pipe, thereby makes the flat surface electrode.When making the electrode of low-resistance value with the material of high resistivity, this is particularly suitable.
Ion-sensitive electrode can be measured (no matter being the aqueous solution or anhydrous solution) ionic activity in the solution, often mentions it in the analytical chemistry field.The measurement of pH value (logarithm of hydrogen ion concentration inverse) is exactly an example, and it is the hydrionic activity of measuring in the solution.For a lot of chemical processes, the pH value is an important parameter.Other example is to measure in the food or the sodium ion in the biological fluid.
Ion-sensitive electrode has cylinder-like shell usually, and the one end seals with ion-sensitive film.This film only allows a kind of iontophoretic injection in the liquor sample to go over, and other material in the solution all cannot get through.In the pipe the inside, there is a device that set potential can be provided, not that the certain solution of composition is exactly that solid conductor contacts with film.Measure from interior point of contact, pass film, thing sample to the second have just been represented the thing sample with reference to the voltage of contact ion(ic)activity.Usually ion-sensitive electrode is made into sphere or flat-section.For the film of vitreousness, ball shaped electrode is than the easier manufacturing of flat-section electrode.Ball shaped electrode is suitable for the liquid towards material and measures in addition, but the amount that measured liquid needs is bigger.In contrast, when detected sample thing comparatively small amt or tested wish maybe to need to use the flats electrode when being moistening solid, film should nestle up the sample thing and needn't immerse in the sample thing this moment.The used film of ion-sensitive electrode has high input resistance for metrical instrument, for example up to 1000～20000 megaohms, thereby but so high impedance meeting makes the interference on the electrode increase the precision that influence is measured.Especially generally all make as the used ion-selective membrane of pH-measuring electrode with glass, for used at ordinary times pH sensing glass, also big more to the big more resistivity in general of hydrionic selectivity.Therefore, the increase of the noise level that caused by the increase owing to resistivity of the improvement of the sensitivity that is obtained from the material is covered.This is the specific question that the flat surface electrode exists.For present flat surface electrode manufacturing technology of habitually practising, the setting range of film thickness (for the material of given resistivity just resistance) has very big restriction.
The ion-sensitive electrode on flat membrane surface generally adopts pickling process and makes, in manufacturing processed, one end of a Glass tubing immerses in the thin-film material melting channel, and the thin-film material of a drip melting state sticks to the end of pipe, has just formed flat membrane after the cooling.The coefficient of expansion of molten glass should with the coefficient of expansion of pipe coupling, be not that pipe break is exactly that film damages so when cooling not simultaneously if these two has bigger, this is inconsistent the causing of shrinkage speed owing to them.In addition, the sealing between pipe and the film usually has defective and is easy to damage.In addition, pickling process also is difficult to control to the homogeneity and the repeatability of film thickness.The variation of film thickness can cause the bigger variation on intensity and resistance value.
As long as after the impregnated pipe cooling, pH glass can be ground to the design thickness that flat membrane requires.Grinding is a kind of time taking operation, and its result is because the unexpected breakage of very thin film makes the disqualification rate of electrode higher.Process of lapping will cause film to produce small pit and bring stress in addition.Thereby the impurity in the abrasive substance also may be embedded into the distortion that grinding part causes film characteristics.At last, the thickness that can be ground and don't can damage is subjected to restriction physically again.This restriction is that the fragility owing to collision phenomenon in the process of lapping and thin-film material causes.This restriction has just hindered us to adopt the glass of low sodium interferential high resistivity in flat or flat substantially film.With regard to the included electrode of prior art, its building block reaches sealing by wave energy.For example, in the U.S. 3,855, in No. 095 patent, yet an interior semicanal of a glass electrode is to adopt the electromagnetic irradn mode via a glass capsulation ring it directly to be sealed with the electrode target near the ion-sensitive spherical shell, with regard to the electrode that has earlier with regard to this or other, prompting or suggestion are not gone to adopt irradiation are had the element of different absorptive character to form interelement sealing method.Therefore, need a kind of novel method of making electrode, it is convenient to utilize improved material to develop good electrode, and the shortcoming that does not have general electrode again and had.
The present invention is a kind of like this ion-sensitive electrode, and it is made of the pipe that can pass the radiating ion-selective membrane and make with the material of energy absorbing radiation of a spherical shell shape.This spherical shell is placed on the pipe, then to the contact surface irradiated heat between pipe and the spherical shell, because pipe is heated to melted state thereby the connection section of pipe and spherical shell is bonding securely.In the concrete device of being introduced, subassembly be by infrared-ray is focused on the pipe end face be lip with the contacted surface of spherical shell on carry out radiation heating.It with tube wall be melted to be enough to film bonding but do not make the degree of film melts.Then pipe slightly like this by gas pressurization (for example general air is as the technology of usually artificial glass-blowing), interface was not only bonded but also reduced bonding stress.
In the concrete device of the present invention who proposes, the diameter of spherical shell is significantly greater than pipe diameter, for example more than two times or two times, when scarce of the part circle of spherical shell inside is placed on the pipe, pipe is facing to the part of sphere, and this part is little with respect to the end face height change of pipe.For example when the diameter of spherical shell was two times of pipe diameter, film exceeded the height of pipe end face less than 1 14 of pipe diameter facing to the part of pipe.Its result, film is planar substantially.
An important feature of this manufacture method is allow to use high resistivity, low sodium interferential material to make film, as to select for use hydrionic selection rate be 10 with respect to the selection rate to sodium ion
13Or bigger material, suggestion is high to 10
14Or it is bigger.This is that its cross section is thinner than the plane electrode film made from general method because the glass that is used on the film can be blow molded into blocky spherical shell.Because the reducing of film thickness, the film made from the higher material of resistivity still has less resistance like this.For example, adopt this technology, flat membrane, lower noise, a low-impedance pH electrode be with a thickness less than 0.025 inch, resistivity is greater than 10
5The glass spherical shell of ohm/cm is made.The sensitivity use range of this electrode can expand pH=14 to.
Below in conjunction with accompanying drawing apparatus of the present invention are described more specifically, therefrom can be done further to understand above-mentioned some characteristics and advantage with other.This installs as shown in drawings, and in all different views in the drawings, same numeral shows same parts.Accompanying drawing is not drawn in proportion, emphasis is placed upon in the explanation to inventive principle.
Fig. 1 is the local amplification profile of the electrode made with pickling process, the technology before it has been described.
Fig. 2 is the parts sectional view of an ion-sensitive electrode.
Fig. 3 is that film is bonded in electrode electrode view in the past, and an infrared source also is shown on the view.
Fig. 3 A is the partial enlarged drawing of Fig. 3.
Fig. 4 is the amplification profile of the working end of the ion-sensitive electrode among Fig. 2 and Fig. 3.
At Fig. 1, show that an employing has the typical flat membrane electrode that the pickling process of former process characteristic is made.Thin-film material 5 is bonded in steeping process on the pipe 8, and its internal surface 6 has irregular profile.This irregular surface can not be revised by grinding, and each electrode that its result produces is all variant, and this has just produced capricious, film high value and that have the hazardous noise level.
At Fig. 2, shown an improved ion-sensitive electrode 10.Electrode 10 has an electrode body 12, and it is round shape normally, and the one end is that flat film 14 seals with one substantially.Electrode body absorbs the spherical film prefabricated component of being spoken of below energy (suggestion infrared absorption) Glass tubing and by one and forms.Using spherical prefabricated component to make electrode just makes the thin-film material making electrode that adopts high resistivity become possibility.The same with general ion-sensitive electrode, the inner solution of being adorned 16 is for providing conductive path between film and the electronic component 18, and electronic component 18 has been measured the potential difference that causes owing to the variation in the sample intermediate ion concentration that solution is housed.
Film 14 is preferably made with hydrogen ion or other ion-sensitive glass, and this glass generally is the mixture of several oxide compounds, and it comprises Lithium Oxide 98min (Li
2O), Cs2O (Cs
2O), lanthanum sesquioxide (La
2O
3), calcium oxide (CaO) and sodium oxide (Na
2O).Also can adopt the material of some other similar composition.In addition, film 14 is made thin, is flat shape basically, and is preferably thick less than 0.025 inch, can be thinned to 0.005 inch.Before this is thinner than far away on the flat membrane ion exchange electrode employed film, therefore can make low noise material, as greater than 10
5The low sodium of ohm/cm resistivity disturbs glass.Although this material has very high resistivity, be about 2.5 * 10
6Ohm/cm, thereby but owing to reduced the growth that thickness has been offset resistivity, its as a result film have moderate resistance.Shu Ru electrical noise greatly reduces and can obtain higher precision in bigger pH scope like this.For example the useful range that can produce the pH value with this method is 0～14 flat membrane electrode.
In order to prevent glass electrode 12, protection tube 20 is housed in its outside in use by accidental damage.This outer sleeve is preferably made with plastelast, and the film end by a shock absorbing rubber lining ring 22 and interior pipe 12 is connected mutually.Thereby lid 24 and draw the other end that lead 26 is installed in electrode and formed a complete member.
The manufacturing processed of electrode shown in Figure 2 is as follows: referring to Fig. 3, prefabricated component 30 is made into round shape, and it has the head 32 of spherical shape, the diameter of this head significantly greater than body 12 will film forming that end.As mentioned above, to pH electrode, can preferentially select for use low sodium to disturb, the high resistivity material that can see through ir radiation is made prefabricated component 30.Reduce the wall thickness of spherical shell 32 then, for example be reduced to about 0.005 inch.For given amount of glass, can control the wall thickness of spherical shell at an easy rate by the change of spherical shell radius (R).
The ratio that changes spherical shell diameter and pipe diameter just can be controlled the flatness of spherical shell.Specifically can be referring to Fig. 3 A, the distance h between spherical film and theoretical planes (h=0) is easy to calculate with formula
h＝1-〔1-cos（sin
-1a）〕/a
Here a is a ratio: r/R
R is the radius of pipe
R is the radius of spherical shell
When ratio a=0.5, h=0.268 * r.In other words, diaphragm seal part and the distance of orifice plane are less than 1 14 of pipe diameter.When a=0.33, this distance is less than 9 percent.
Although the thickness of spherical shell is very little, certain intensity is arranged, not only firm but also be easy to process comparatively speaking.The profile that arches upward has slightly in addition increased intensity again, this be because the ultimate compression strength of glass greater than tensile strength.The flat board of same thickness is very easy to crisp and also is difficult to processing.Besides spherical shell has relatively consistent wall thickness, and therefore, the thickness of film is resistance Be Controlled better just.
Prefabricated component 30 is placed on an end of electrode 12, makes spherical shell directly be enclosed within the edge of pipe 12.As mentioned above, the ultrared glass of pipe 12 the most handy absorptions is made.Usually, heat absorbing glass is called as " green chloroplast glass ".For example NEC glass company, and Japanese KAKVDA-CHO, KITADV, " SRI " glass of Osaka company limited manufacturing and " STI " glass also have some glass that Schoot company makes as Schoot No4840E glass.
The next step of making electrode is the intersection that the radiation laser beam from infrared source 15 is focused on the end 12A of spherical shell 32 and pipe 12.Light only have any to be absorbed thereby heat slightly a bit, and the edge that heat absorbing glass pipe 12 contacts with film is heated equably by can see through infrared spherical shell 32 time.Meanwhile, turne tube is to keep the homogeneity of heating.Radiation focuses on the interface, and the result makes the edge fusing of pipe therefore pipe and film welding.Remove infrared radiation source (promptly shutting power supply).Should be noted that the fusing point of pipe glass is lower than the fusing point of film spherical shell, otherwise in fusion process, the film spherical shell may be softened and damage.
When subassembly begins to cool down, in pipe 12, pressurizeed slightly so that impel position, seal junction 34(Fig. 4 who is present in uniformly between glass electrode and the film 14 of generation in its space).The light pressure of this air chamber also can be eliminated the internal stress that increases owing to bonding process on film 14 and the combining site 34.
After by bonding subassembly cooling, unnecessary thin-film material must break and fall down.Only need polish the uneven edge of bonding subassembly upper film 14 then, so that can be used fully.The major part of thin-film material is not only thin but also do not have and support, and needn't polish and grinding.At any time can do last assembling to the electrode 12 that has welding thin-film material 14 then, electrode member 18 is inserted in the electrode body, until the other end of shell.
The modified version ion-sensitive electrode of making of said process was compared with former flat surface ion-sensitive pH electrode good performance.As mentioned above, in fact this manufacturing process makes the thickness of flat membrane little of 0.005 inch, therefore allows to use the thin-film material of the resistivity that manys higher than existing thin-film material.Like this, rather desirable but have high resistivity so far again and cause some high performance materials of the contradiction that noise increases just can be used for being manufactured on the pH electrode of working in the very wide pH scope effectively concerning having the such characteristics of low sodium disturbing influence.
This manufacturing processed also has the advantage of wall thickness height unanimity, and this obtains when the blow-molded glass ball.The spheroid of blowing out with thin-film material 32 has desired uniform wall thickness, and result's formed film on pipe 12 also has the characteristics of uniform wall thickness.This has just been avoided the undesirable variation of electrode impedance, can be referring to the explanation of Fig. 1.
Adopt this method that film is structurally also improved.Even combination between pipe 12 and the film 14 is very firm, and that separates may be compared with much smaller with the formed combining site of the past method.In addition, also safety has been eliminated the small scar that produced when usually film surface being ground to the desired thickness of flat membrane and stress after on the pipe that the film spheroid is bonded to electrode probe, does not need it is further processed.This just makes improved film surface seldom can cause breaking of electrode.
At last, should be noted that the method that is adopted can reduce manufacturing expense significantly when making this modified version ion-sensitive electrode.Because in fact cancelled hand lapping and polished this when when making the flat surface ion-sensitive electrode, taking a lot of work most and the most thorny operation.The waste that causes owing to film breaks in this external grinding and the polishing is also avoided thereupon.
Though the present invention has been done concrete diagram and description with reference to its most preferred embodiment, but much less, to those skilled in the art, may not break away under the present invention's spirit and the situation by the invention scope that appended claims limited, make the many variations of form and details aspect.For example, it is fully possible using other electromagnetic-energies to come welding electrode body and film as UV-light.The material that constitutes probe in addition is not only limited to glass material yet, and pottery and Resins, epoxy also can be used in the ion-sensitive electrode device and good effect is arranged.Under suitable situation, promptly under thin-film material and pipe wall material are not compatible fully situation each other, can use one not only desirable bonding to realize with tube wall but also the fusible adhesives in centre compatible with film.
Claims (14)
1, a kind of method of utilizing electromagnetic radiation to make the ion-sensitive electrode body, this method may further comprise the steps:
A. a kind of pipe one end as electrode body is inserted in the spherical shell as ion sensitive membrane, the end that makes described pipe contacts with the internal surface of described spherical shell; And
A kind of radiation is shone on that end with the described pipe of described spherical housing contacts by described spherical shell, the described end of described pipe is fused to the internal surface of described spherical shell, it is characterized in that: described pipe mainly adopts and can absorb predetermined wavelength radiating material and described spherical shell mainly adopts basically and can see through described predetermined wavelength radiating material.
2, method according to claim 1 is characterized in that described predetermined wavelength is in the infrared region.
3, method according to claim 1, the thickness that it is characterized in that described spherical shell is less than 0.025 inch.
4, method according to claim 1 is characterized in that further comprising the steps of:
The described electrode body of light pressure is described to the internal stress in the pipe of infrared ray responsive to eliminate after described pipe is fused to described spherical shell.
5, method according to claim 1 is characterized in that described ion-sensitive film material selection and can see through hydrionic material.
6, method according to claim 1, thus it is characterized in that used ion-sensitive film material comprises that the finite part of a described spherical case surface forms a flat substantially surface.
7, method according to claim 6, the radius that it is characterized in that used spherical shell is the twice of described pipe radius at least.
8, a kind of low-resistance ion-sensitive electrode of making according to the described method of claim 1, it comprises spherical shell shape ion sensitive membrane and hollow edged electrode body, it is characterized in that described spherical shell shape ion sensitive membrane is by making through predetermined wavelength radiating thin-film material; And described hollow edged electrode body is made by absorbing predetermined wavelength radiating material.
9, ion-sensitive electrode according to claim 8 is characterized in that described spherical shell shape ion sensitive membrane is one and constitutes flat ion-sensitive surface.
10, ion-sensitive electrode according to claim 8, the thickness that it is characterized in that described ion sensitive membrane is less than 0.025 inch.
11, ion-sensitive electrode according to claim 8 is characterized in that described thin-film material is littler of being the latter's 1/10 at least than the ion of concentration to be measured to the sodium ion susceptibility.
12, ion-sensitive electrode according to claim 8 is characterized in that described ion-sensitive film is made of the thin-film material that can see through ir radiation.
13, ion-sensitive electrode according to claim 8 is characterized in that described hollow edged electrode body made by infrared absorbing material.
14, ion-sensitive electrode according to claim 8 is characterized in that described electrode is to the hydrogen ion sensitivity in order to the measurement ion(ic)activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85107084 CN1008181B (en) | 1984-09-05 | 1985-09-23 | Improved ion-sensitive electrode |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64759984A | 1984-09-05 | 1984-09-05 | |
| CN 85107084 CN1008181B (en) | 1984-09-05 | 1985-09-23 | Improved ion-sensitive electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85107084A CN85107084A (en) | 1987-04-01 |
| CN1008181B true CN1008181B (en) | 1990-05-30 |
Family
ID=25742068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107084 Expired CN1008181B (en) | 1984-09-05 | 1985-09-23 | Improved ion-sensitive electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008181B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351098B (en) * | 2013-06-25 | 2015-09-09 | 广东格斯泰气密元件有限公司 | A kind of sealing glass for compressor terminal and manufacture method thereof |
| EP3594671B1 (en) * | 2018-07-10 | 2022-09-07 | ABB Schweiz AG | Method for monitoring the sensor function of a potentiometric sensor and corresponding potentiometric sensor assembly |
-
1985
- 1985-09-23 CN CN 85107084 patent/CN1008181B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85107084A (en) | 1987-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0127438B1 (en) | Diagnostic device incorporating a biochemical ligand | |
| US8445263B2 (en) | Device for cellular electrophysiology sensor, cellular electrophysiology sensor using the device, and method for manufacturing the cellular electrophysiology sensor device | |
| CN101769876A (en) | Method for carrying out failure analysis in semiconductor device | |
| US4681116A (en) | Antimony electrode assembly and method of manufacture, and use thereof | |
| US3933612A (en) | Glass electrode structure for radio capsule | |
| US3282817A (en) | Glass electrode and method of making the same | |
| CN1311234C (en) | PH glass membrane and sensor | |
| CN1008181B (en) | Improved ion-sensitive electrode | |
| US20050145330A1 (en) | Transmission laser welding of electro-chemical sensors | |
| US4687500A (en) | Method for manufacturing an ion-sensitive electrode | |
| CA1242764A (en) | Ion-sensitive electrode | |
| US8329451B2 (en) | Cell electrophysiological sensor and method for manufacturing the same | |
| US4661236A (en) | Fluid electrode and method of making | |
| Moe | Reference electrodes for nonaqueous and corrosive media | |
| US3923625A (en) | Reinforced glass electrode structure | |
| US20060096975A1 (en) | Method and apparatus for treating glass bodies, as well as a glass body and measuring probe | |
| US4459199A (en) | Ruggedized ion-responsive electrode and its manufacturing process | |
| US5589085A (en) | Process of manufacturing a detecting unit for an electrolytic cell with thin film electrodes | |
| JP7408810B2 (en) | Ion sensor manufacturing method | |
| GB2182446A (en) | Antimony electrode assembly | |
| CN111537580A (en) | Sensing electrode based on optical fiber bundle and preparation method and application thereof | |
| US20240166554A1 (en) | Apparatus and method for forming a membrane | |
| US3415731A (en) | Glass electrodes and method for producing the same | |
| EP0193909A2 (en) | Improved ion-sensitive flat surface electrode | |
| CN110328211B (en) | Separation method and chemical reagent for separating nonmetal sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |