GB1602564A - Apparatus for detecting elements - Google Patents
Apparatus for detecting elements Download PDFInfo
- Publication number
- GB1602564A GB1602564A GB23016/78A GB2301678A GB1602564A GB 1602564 A GB1602564 A GB 1602564A GB 23016/78 A GB23016/78 A GB 23016/78A GB 2301678 A GB2301678 A GB 2301678A GB 1602564 A GB1602564 A GB 1602564A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alumina
- tube
- fused
- pellet
- sealed
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 76
- 239000008188 pellet Substances 0.000 claims description 37
- 239000000523 sample Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 230000004927 fusion Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000012925 reference material Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 239000011819 refractory material Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- -1 thalium Chemical compound 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 230000000007 visual effect Effects 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000971 Silver steel Inorganic materials 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001651 emery Inorganic materials 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
Description
(54) IMPROVED APPARATUS FOR DETECTING
ELEMENTS
(71) We, NATIONAL RESEARCH
DEVELOPMENT CORPORATION, a
British Corporation established by Statute of
Kingsgate House, 66-74 Victoria Street,
London S.W.I, do hereby declare the invention for which I pray that a patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to an improved apparatus for the detection and determination of small quantities of single elements normally in the presence of other materials and in particular to the detection and determination of impurities of specific elements in solid or molten metals or alloys.
There are numerous industrial applications where it is advantageous to be able to measure simply and quickly the levels of such impurities. For example, in the field of metallurgical refining it is often desirable to estimate impurities whilst the metal is still in the molten state, so that the composition may be adjusted before it is cast.
The specification of our United Kingdom
Patent No. 1470558 describes a method and apparatus for the detection or determination of an element in a substance comprising that element by monitoring the e.m.f. generated between the substance and reference material, in which the reference material is a solid electrolyte comprising a alumina containing said element or a solid compound of said element separated from the substance by said electrolyte. In a preferred embodiment, the apparatus of
U.K. Patent No. 1470558 takes the form of a probe comprising a tube of refractory material sealed at one end with a pellet comprising alumina containing the element in question. A problem which had been associated with similar tubular probes in the prior art and which is acknowledged in the specification of U.K. Patent No.
1470558 is the tendency to failure of the seal between the refractory tube and alumina electrolyte pellet, particularly when used in the extreme high temperature environment of molten metals. The solution to this problem proposed in the above patent specification includes the use of a solid reference material and, in addition, in preferred embodiments, formation of the p alumina pellet in situ in the end of the tube by hot pressing of powder comprising p alumina.
The present invention relates to improvements in the method of manufacture and structure of the preferred tubular probes of UK Patent No. 1470558 which further enhances their reliability and performance.
Accordingly the present invention comprises a process for the manufacture of apparatus for use in the detection or determination of an element in a substance comprising said element, in which p- alumina containing said element is fused into the end of a tube of a refractory material to provide a tubular probe sealed at one end with a pellet comprising said p alumina, and in which the sealed end of said tube is rapidly quenched to ambient temperature after fusion treatment.
The invention also includes apparatus, comprising a tube of refractory material sealed at one end with a pellet comprising a p-alumina, when produced by a process according to the invention.
Generally the areas of application and use, the type and composition of materials for construction, overall structure and dimensions of the tubular probes of the present invention are the same or similar to those of the preferred tubular probes comprising a tube of refractory material sealed at one end with a pellet comprising a-alumina, as described in the specification of UK Patent No. 1470558. Thus, for example, the probes of the invention may be used to detect elements which for p aluminas, including lithium, potassium, rubidium, copper, silver, thalium, indium and gallium and particularly sodium, especially for detection of these elements in the environment of molten metals, such as molten aluminium.Preferred electrolyte A- alumina phases comprise mixtures of the A- alumina with alumina such that the molar ratio of Awl203 to the metal oxide is in the range from 11:1 up to 12:1. Also, preferably, there is a reference material separate from the alumina electrolyte pellet especially comprising a alumina containing the element under determination usually in the form of a 2 phase material e.g. a mixture of ss- and A"-alumina or a mixture of ,B and aalumina. Furthermore optimum sizes for the alumina pellet are of diameter from 1/8" to 1/4" or especially about 3/16".
It will be appreciated,that certain of the jB-aluminas mentioned above, for instance, copper, silver, thalium, indium and gallium p-aluminas, are liable to decompose at the fusion temperatures required to form the seal between pellet and refractory tube.The probes of the invention comprising such ,B- alumina solid electrolyte phases may, however, be manufactured by first fusing a material containing a alumina of suitable thermal stablility e.g. potassium or preferably sodium alumina, to form a pellet comprising the thermally stable p- alumina sealed in the end of the refractory tube, after which the thermally stable F alumina is converted to the alumina of choice, for instance, by ion exchange.
The alumina containing material which is fused into the refractory tube to provided the solid electrolyte pellet may be in any suitable physical form and may include preformed pellets of alumina containing material. More conveniently, however, powder containing alumina is used and is used to form a solid pellet in situ in the end of the refractory tube.
Fusion of the alumina containing material e.g. preformed pellet or preferably powder, to form the pellet in the end of the refractory tube may be achieved by any suitable heating cycle, and temperature of up to white heat may be used. For instance, powder comprising alumina e.g. a mixture of a- and p-alumina, is compacted by hand into the end of a suitable refractory tube e.g. a silica tube, and the end of the tube is heated in a flame, such as a natural gas/oxygen flame, until satisfactory fusion of the alumina powder has taken place to form a/3- alumina pellet sealing the end of the tube.
This method of constructing the tubular probes is advantageously quick and simple
and may be easily adapted for
manufacturing scale production. It is important, however, to control the amount of fushion which takes place; insufficient
fusion may give a poor seal between pellet
and tube, whereas excessive fusion treatment may completely melt the F alumina containing material and disrupt the pellet. In practice it has been found to be possible to judge the correct extent of fusion treatment by a straight-forward visual check. For example, it is normally satisfactory to ensure that the fusion treatment has been carried on for a sufficient period of time to produce a continuous band of fused material encircling the pellet in the end of the tube.
This fused band is seen as a bright circle of light when the heated end of the tube is viewed by eye through dark glasses. In a manufacturing environment the correct period of fusion treatment may be readily ascertained by experiment, and a standardised fusion treatment period then used.
In the method of manufacturing the tubular probes, according to the present invention, the tubes are quenched rapidly to ambient temperature subsequent to the fusion treatment. Preferably the tubes are allowed to cool to red heat, especially a dull red heat, prior to the rapid quenching.
Rapid quenching may for example, be achieved by plunging the red-hot end of the probe into cold water. Suprisingly, it has been found that this rapid quenching treatment gives rise to a alumina pellet having a particularly good seal with the refractory tube and highly satisfactory conductivity characteristics.
Subsequent to fusion treatment and quenching any undesirable fused layer coating the external surface of the pellet may be removed, for instance, by grinding to advantageously expose the alumina for enhanced electrical conductivity.
Solid reference material, such as the preferred a//3 or pss" mixtures, may then be layered on top of the electrolyte pellet within the tubular probe. An internal electrode, such as stainless steel rod preferably sharpened at its end, may then be inserted into the tube to make electrical contact with the internal surface of the ,B- alumina electrolyte, either directly or indirectly through a conductive reference material. Such an internal electrode is usually sealed into the tube, for instance, by means of a suitable cement, such as a heat resistance cement, applied around the end of the tube remote from the electrolyte pellet.
As is acknowledged in the specification of
U.K. Patent No. 1470558, the activity of the element in the alumina reference e.g. the sodium in the sodium p-alumina, is dependent to some extent upon the oxygen potential of the atmosphere over the reference material. It has recently been found, in particular when using probes in which a metal rod internal electrode is sealed into the tube, that the e.m.f. obtained may be variable, and it is believed that this is due to the oxygen potential of the atmosphere varying as a result of oxygen reacting with the metal electrode.
Accordingly therefore, in a preferred embodiment of the invention, the sealed tubular probe contains, preferably on top of the layer of reference material, a layer of second solid material which provides a fixed oxygen potential i.e. partial pressure at a given temperature, within the sealed probe.
Preferably a layer of material comprising a metal/metal oxide mixture used, such as a
Cu/Cu2O Cr/CrzO3 or especially Ni/NiO mixture. It has been found that use of such metal/metal oxide mixtures in the probes of the invention helps to ensure fast reaction times e.g. in the order of a few seconds, and stable responses over extended periods of time.
An improved apparatus according to the present invention and its method of manufacture are now described by way of example with reference to the accompanying diagrams.
Sodium alumina electrolyte powder consisting of sodium alumina (Na2O. 11 Awl203) with a small excess of a-A12O3 is lightly compacted by hand into one end of a silica tube 1 (length 8 cm, external diameter 4 mm, internal diameter 2mm) to a depth of about 2-3 mm. This end of the silica tube 1 is then held in a natural gas-oxygen flame and the sodium alumina electrolyte powder fused to give sodium alumina electrolyte pellet 2 sealing one end of the tube 1.The correct period for the fusion treatment is judged by careful visual observation through dark glasses of the heated end of the silica tube, the treatment being continued until a brightly luminous continuous band of fused material is seen to encircle the alumina pellet 2. The end of the tube 1 is then removed from the flame and allowed to cool to a dull red heat at which time it is rapidly quenched by plunging into cold water. The external fused surface coating of the alumina electrolyte pellet 2 is then removed by grinding against emery paper, the end of the silica tube 1 being slightly bevelled around its end edge.
A 1:1 mixture of powdered a- and - alumina is then introduced into tube 1 via its open end and packed down to give a layer of 2 phase a-//3-alumina reference material 3 to a depth of about 10 mm. A similar amount of powdered 1:1
NickelNickel oxide mixture is packed on top of the layer of reference material 3 to provide a layer of material 4 which stabilises the oxygen potential within the probe during use. It will be appreciated however, that the relative proportions of metal and metal oxide in the oxygen potential stabiliser 4 are not critical and may be varied widely. The layer of reference material 3 and oxygen potential stabiliser 4 are finally rammed home with a silver steel rod 5 (length 8 mm, diameter 2 mm), which has been ground to a point at its end and which provides an internal electrode.The probe is then made airtight by sealing the rod 5 into the open end of the tube 1 with "Autostic" heat resistant cement 6.
The probe as constructed above is connected across a suitable meter, such as a high impedance voltmeter, with an external electrode (not shown) and provides a highly reliable probe with a fast reaction time and stable response for measurement of sodium, particularly in the environment of molten metals, such as molten aluminium.
WHAT WE CLAIM IS:
1. A process for the manufacture of apparatus for use in the detection or determination of an element in a substance comprising said element, in which p- alumina containing said element is fused into the end of a tube of refractory material to provide a tubular probe sealed at one end with a solid electrolyte pellet comprising said p-alumina, and in which the sealed end of said tube is rapidly quenched to ambient temperature after fusion treatment.
2. A process according to Claim 1, for the manufacture of apparatus comprising a copper, silver, thalium, indium or gallium A- alumina containing solid electrolyte pellet, in which a material containing a thermally stable alumina is fused into the end of the tube of refractory material to provide a tubular probe sealed at one end with a pellet comprising said thermally stable p-alumina, after which the thermally stabled alumina is converted to copper, silver, thalium, indium of gallium alumina by Ion exchange.
3. A process according to Claim 1 or 2, in which powder comprising alumina is fused into the end of the tube of refractory material.
4. A process according to Claim 1, 2 or 3, in which the alumina containing material is fused into the end of the tube of refractory material by heating the said end of the tube in a flame until a continuous band of fused material encircles the A- alumina containing material.
5. A process according to any of Claims 1--4, in which the alumina containing material is fused in a flame, and the heated end of the tube is allowed to cool to red heat at which time it is rapidly quenched to ambient temperature by plunging into cold water.
6. Apparatus comprising a tube of refractory material sealed at one end with a pellet comprising a alumina when
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
1. A process for the manufacture of apparatus for use in the detection or determination of an element in a substance comprising said element, in which p- alumina containing said element is fused into the end of a tube of refractory material to provide a tubular probe sealed at one end with a solid electrolyte pellet comprising said p-alumina, and in which the sealed end of said tube is rapidly quenched to ambient temperature after fusion treatment.
2. A process according to Claim 1, for the manufacture of apparatus comprising a copper, silver, thalium, indium or gallium A- alumina containing solid electrolyte pellet, in which a material containing a thermally stable alumina is fused into the end of the tube of refractory material to provide a tubular probe sealed at one end with a pellet comprising said thermally stable p-alumina, after which the thermally stabled alumina is converted to copper, silver, thalium, indium of gallium alumina by Ion exchange.
3. A process according to Claim 1 or 2, in which powder comprising alumina is fused into the end of the tube of refractory material.
4. A process according to Claim 1, 2 or 3, in which the alumina containing material is fused into the end of the tube of refractory material by heating the said end of the tube in a flame until a continuous band of fused material encircles the A- alumina containing material.
5. A process according to any of Claims 1--4, in which the alumina containing material is fused in a flame, and the heated end of the tube is allowed to cool to red heat at which time it is rapidly quenched to ambient temperature by plunging into cold water.
6. Apparatus comprising a tube of refractory material sealed at one end with a pellet comprising a alumina when
produced by a process according to any of
Claims 1--5.
7. Apparatus according to Claim 6, in which an internal electrode is sealed into the refractory tube which contains, in addition, to reference material, a second solid material to provide a fixed oxygen potential within sealed probe.
8. Apparatus according to Claim 7, in which the second solid material comprises a metal/metal oxide mixture.
9. Apparatus according to Claim 8, in which the second solid material comprises a Cu/Cu,O, Cr/Cr2O3 or Ni/NiO mixture.
10. Apparatus according to any one of
Claims 6--9 substantially as hereinbefore described and illustrated with particular reference to the specific description and accompanying diagram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB23016/78A GB1602564A (en) | 1974-07-03 | 1978-05-26 | Apparatus for detecting elements |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2949074A GB1470558A (en) | 1974-07-03 | 1974-07-03 | Method and apparatus for detecting elements |
| GB23016/78A GB1602564A (en) | 1974-07-03 | 1978-05-26 | Apparatus for detecting elements |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1602564A true GB1602564A (en) | 1981-11-11 |
Family
ID=26256248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB23016/78A Expired GB1602564A (en) | 1974-07-03 | 1978-05-26 | Apparatus for detecting elements |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1602564A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0400813A2 (en) * | 1989-05-01 | 1990-12-05 | General Electric Company | Reference electrode probe |
| US5192404A (en) * | 1988-10-06 | 1993-03-09 | Mineral Industry Research Organisation | Method for measuring a minor element in a molten metal |
| US5336389A (en) * | 1992-06-08 | 1994-08-09 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Long lasting alkali and alkaline earth metal sensor |
| US6805781B2 (en) | 2000-03-01 | 2004-10-19 | Radiometer Medical A/S | Electrode device with a solid state reference system |
-
1978
- 1978-05-26 GB GB23016/78A patent/GB1602564A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192404A (en) * | 1988-10-06 | 1993-03-09 | Mineral Industry Research Organisation | Method for measuring a minor element in a molten metal |
| EP0400813A2 (en) * | 1989-05-01 | 1990-12-05 | General Electric Company | Reference electrode probe |
| EP0400813B1 (en) * | 1989-05-01 | 1994-08-24 | General Electric Company | Reference electrode probe |
| US5336389A (en) * | 1992-06-08 | 1994-08-09 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources | Long lasting alkali and alkaline earth metal sensor |
| US6805781B2 (en) | 2000-03-01 | 2004-10-19 | Radiometer Medical A/S | Electrode device with a solid state reference system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Boyd et al. | Effect of pressure on the melting of diopside, CaMgSi2O6, and albite, NaAlSi3O8, in the range up to 50 kilobars | |
| Cammenga et al. | The temperature calibration of scanning calorimeters: Part 2. Calibration substances | |
| US3773641A (en) | Means for determining the oxygen content of liquid metals | |
| US4406754A (en) | Method and probe for the rapid determination of sulfur level | |
| Stubbs et al. | The In-In2S3 System1 | |
| US3864232A (en) | Apparatus for Monitoring the Oxygen Content of High Temperature Fluids | |
| CN105806504A (en) | High-temperature-resistant cheap metal armored thermocouple and manufacturing method thereof | |
| GB1381976A (en) | Apparatus for measuring oxygen content of a fluid | |
| GB1602564A (en) | Apparatus for detecting elements | |
| US4007106A (en) | Device for measuring oxygen concentration in molten-metal | |
| US5232286A (en) | Long lasting thermocouple for high temperature measurements of liquid metals, mattes and slags | |
| US4166009A (en) | Method for detecting elements | |
| CA2285943C (en) | Probe for detection of the concentration of various elements in molten metal | |
| US4217179A (en) | Determination of lithium, sensor therefor and method of making said sensor | |
| US3980543A (en) | Electrochemical cell structure | |
| GB1594223A (en) | Determination of hydrogen | |
| CN108034876A (en) | A kind of clinical thermometer mercury-free liquid alloy and clinical thermometer | |
| GB2025626A (en) | Lithium determination | |
| KR101190592B1 (en) | Solid electrolyte tube and sensortip for measuring sulfur concentration of high temperature melting material comprising the same | |
| US4035277A (en) | Oxygen probe | |
| Flengas et al. | VOLTAIC CELLS IN FUSED SALTS: PART III. THE SYSTEM SILVER–SILVER CHLORIDE, CADMIUM–CADMIUM CHLORIDE | |
| CN106967916B (en) | The liquid alloy and the preparation method and application thereof of alternative mercury | |
| Hayward | The Pressures and Temperatures Developed During the Reduction of Uranium Tetrafluoride by the Bomb Method | |
| Okajima et al. | Measurements of Activities of Silver in Silver-Bismuth Molten Alloys by the TIE Method | |
| CN212409897U (en) | Armored thermocouple structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19950701 |