US3679976A - Elapsed time indicator having color indication - Google Patents

Elapsed time indicator having color indication Download PDF

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Publication number
US3679976A
US3679976A US127193A US3679976DA US3679976A US 3679976 A US3679976 A US 3679976A US 127193 A US127193 A US 127193A US 3679976D A US3679976D A US 3679976DA US 3679976 A US3679976 A US 3679976A
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US
United States
Prior art keywords
indicator
electrolytic solution
elapsed time
coloring
envelope
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 - Lifetime
Application number
US127193A
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English (en)
Inventor
Juro Ogawa
Fujimoto Yoshiaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Radio Co Ltd
Original Assignee
Japan Radio Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2755770A external-priority patent/JPS4938188B1/ja
Priority claimed from JP9854370A external-priority patent/JPS5010750B1/ja
Application filed by Japan Radio Co Ltd filed Critical Japan Radio Co Ltd
Application granted granted Critical
Publication of US3679976A publication Critical patent/US3679976A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G04—HOROLOGY
    • G04F—TIME-INTERVAL MEASURING
    • G04F13/00—Apparatus for measuring unknown time intervals by means not provided for in groups G04F5/00 - G04F10/00
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R22/00—Arrangements for measuring time integral of electric power or current, e.g. electricity meters
    • G01R22/04—Arrangements for measuring time integral of electric power or current, e.g. electricity meters by calorimetric methods
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07C—TIME OR ATTENDANCE REGISTERS; REGISTERING OR INDICATING THE WORKING OF MACHINES; GENERATING RANDOM NUMBERS; VOTING OR LOTTERY APPARATUS; ARRANGEMENTS, SYSTEMS OR APPARATUS FOR CHECKING NOT PROVIDED FOR ELSEWHERE
    • G07C3/00—Registering or indicating the condition or the working of machines or other apparatus, other than vehicles
    • G07C3/02—Registering or indicating working or idle time only

Definitions

  • the anode electrode of an elapsed time indicator includes an elapsed time measuring metallic element superposed on a coloring metallic element, the normal electrode potential of the coloring element being higher than that of the elapsed time measuring element, and lower than the electrolyzing potential of the electrolytic solution, so that electrolysis of the elapsed time measuring element precedes that of the coloring element.
  • the electrolytic solution contains a substance which reacts with the coloring element on electrolysis thereof to change the color of the electrolytic solution, thereby indicating the elapsed time.
  • Elapsed time indicators of the electrolytic type employing the principle of electroplating in accordance with Faradays law are well known in the art as comprising an anode, a cathode and an electrolytic solution housed in a sealed transparent envelope, the main constituent of the electrolytic solution being a salt of the same metal as the anode metal.
  • a reduction of the anode length and an extension of the cathode length is effected by applying a direct current between the electrodes and the elapsed time during which the current is flowing can be determined as a function of the reduction in length of the anode or the increase in length of the cathode by means of a scale on the envelope.
  • Another type of known elapsed time indicator which is improved relative to the aforementioned prior art indicator comprises an electrolytic solution enclosed in a narrow tube, both ends of which are sealed with mercury.
  • this indicator has the disadvantage that it is fragile against mechanical vibrations and that the cost thereof is very high.
  • Another type of known elapsed time indicator includes an anode which comprises an electrolyzable metallic element and a non-electrolyzable metallic element.
  • the internal resistance of the indicator increases substantially at the ending stage when the entire electrolyzable element has been completely electrolyzed, so that the voltage between the anode and the cathode is rapidly increased, which can be indicated by means of a meter or an alarm in an external circuit.
  • the warning of the predetermined lapse of time is available.
  • the cost increases due to the necessity of providing an external indicating circuit.
  • an overvoltage can be applied to the elapsed time indicator so that the pressure within the envelope increases due to the bubbles generated by the electrolysis in the electrolytic solution. This can cause unexpected damage such as breakage of the envelope or leakage of the electrolytic solution from the envelope.
  • the conventional elapsed time indicators described above have a common disadvantage in that the elapsed time can be observed or determined only by viewing the indicator from the outside.
  • the main object of the present invention is to provide an elapsed time indicator which avoids the disadvantages and the difficulties of the prior art indicators as discussed above.
  • the present invention is directed to an elapsed time indicator wherein when electrolysis has proceeded until a predetermined time has elapsed, the electrolytic solution is caused to color, or discolor, so that it may be readily determined when a predetermined period of time has elapsed.
  • an elapsed time indicator includes an envelope containing an electrolytic solution, an anode electrode and a cathode electrode housed therein.
  • the anode electrode comprises an elapsed time measuring metallic element and a coloring metallic element superposed on one another, the normal electrode potential of the coloring metallic element being higher than that of the elapsed time measuring metallic element, and lower than the electrolyzing potential of the electrolytic solution, so that electrolysis of the elapsed time measuring metallic element preceeds that of the coloring metallic element.
  • the electrolytic solution contained in the envelope includes a substance which reacts with the elapsed time indicators, to an electrolytic color indicating coloring metallic element on electrolysis thereof, so that electrolysis of the coloring metallic element cause the color of the electrolytic solution to change.
  • the electrolytic solution is caused to change color to thereby indicate the elapsed period of time.
  • the anode electrode may comprise two kinds of metallic elements whose normal electrode potentials relative to the electrolytic solution are different. It is also known to use the first metallic anode element to measure the elapsed time, and to use the second metallic element as the supporting element for the first metallic element. The second metallic element used only as the supporting element and is not to be electrolyzed. Therefore, it has been preferable that the normal electrode potential of the first metallic anode element relative to the electrolytic solution is selected to be lower than the electrolyzing potential of the water in the electrolytic solution, while that of the second metallic element is selected to be higher than the electrolyzing potential of the water.
  • electrolysis of the first and second metallic elements in accordance with Faraday's law takes place successively by selecting the normal electrode potential of the second metallic element relative to the electrolytic solution to be higher than that of the first metallic element and to be lower than the electrolyzing potential of the water in the electrolytic solution. That is, the first metallic element is first electrolyzed so as to serve as an elapsed time measuring element, while the second metallic element is then electrolyzed as a discoloring element after the elapsed time measuring element has been electrolyzed. Electrolyzing of the second metallic element causes discoloring or coloring of the electrolytic solution.
  • the composition of the electrolytic solution must be such that it is not discolored nor colored by the electrolysis of the first elapsed time measuring metallic element.
  • the electrolytic solution of the color indicating timer includes a ligand, in the form of a salt with the elapsed time measuring metal ions, which can produce a deep color complex by coordinating with the discoloring metal ions which are produced in the electrolytic solution at the time of electrolysis of the second coloring metallic element.
  • the time required for the complete electrolysis of the first elapsed time measuring metallic element can be chosen by selecting the mass of the elapsed time measuring metallic element in accordance with the magnitude of the direct current in accordance with F aradays laws.
  • no ligand is contained in the electrolytic solution.
  • the plating solution for the elapsed time measuring metal of which the main constituent is a salt of said elapsed time measuring metal is used as the electrolytic solution.
  • a coloring agent is added to the solution beforehand and the coloring metal ions react with the coloring agent at the time when the coloring metal (i.e., the second metallic element) is electrolyzed. The reaction results in discoloring or coloring of the electrolytic solution.
  • the elapsed time indicator of the present invention includes an envelope containing an anode which comprises an elapsed time measuring metallic element (first metal) 1 superposed on a coloring metallic element (second metal) 2. Elements 1 and 2 may be secured I together by welding, bonding, or the like.
  • the entire anode is supported by an anode supporting metallic element 3 welded or otherwise secured to a surface of the coloring metallic element 2, which surface is not welded with the elapsed time measuring metallic element 1.
  • a cathode element 4 the surface of which is exposed to the electrolytic solution preferably being coated with, for example, silver to improve the electrodeposition of the elapsed time measuring metal I on the cathode 4.
  • the anode support element 3 and the cathode 4 are preferably supported in the envelope 5 by means of an insulating member 11.
  • the envelope 5 comprises a transparent or semi-transparent material such as, for example, glass or an organic macro-molecular material such as polyethylene, polyester or epoxide resin.
  • the external surface of the envelope 5 can be provided with a transparent or semitransparent protective film 6 made of, for example, a rubber material such as silicone rubber. The protective film is used to protect the envelope 5 against mechanical shocks. Even if the envelope is broken, the leakage of the electrolytic solution from within the envelope can be inhibited by the film 6.
  • a base 7 is connected to the envelope 5 and is electrically connected to the cathode 4.
  • the protective film 6 can be so formed that the external surface of the envelope 5 and the marginal part of the base 7 adjacent the envelope 5 are coated with liquid silicone rubber by spraying and drying, for example. In this manner, the upper marginal part of the base 7 and the lower marginal part of the envelope 5 are air-tightly sealed to each other.
  • the anode support element 3 is electrically connected to a contact 8 at the end of base 7. Contact 8 is insulated from base 7 by an insulator l0.
  • a bubble 9 (or foamed styrene) is contained together with the electrolytic solution in the envelope 5 to inhibit the increase of internal pressure. If there was no bubble 9 contained in the envelope 5, an intensive internal pressure from the inside of the envelope, which can be produced by the expansion of the electrolytic solution or its change to the gaseous state due to increase in temperature in the atmosphere outside the envelope, could cause the envelope 5 to explode.
  • the contained bubble 9 is useful to avoid such dangerous accidents. Even if the temperature in the atmosphere outside the envelope increases up to 130 C, the temperature of the electrolytic solution in the envelope will not increase to such a degree that will cause the electrolytic solution to evaporate. This is because the bubble 9 inhibits an excessive increase of internal pressure.
  • the size of the bubble can preferably be selected to be more than 2 percent in volume relative to the volume of the electrolytic solution contained in envelope 5.
  • the diameter of the bubble 9 can be about 4mm for a normal sized envelope.
  • a bubble of 1 atm. air is contained in the envelope.
  • a bubble including a gas without oxygen, such as, for example, nitrogen, can also be used with a favorable effect.
  • the coloring metallic anode element 2 and the elapsed time measuring metallic element are secured together by welding in the gaseous current of hydrogen in an electric furnace or by supersonic welding to form an alloy junction region of ca. 20A. thick at the contact surfaces thereof.
  • This junction region prevents the contact surfaces between elements I and 2 from being electrolyzed before the elapsed time measuring metallic element 1 is completely electrolyzed, so that the accuracy in elapsed time measurement can be maintained.
  • a ligand such as, for example, thiocyanate ions, cyanate ions, hydroxide ions, ammonium ions, chlorine ions, nitrate ions or thiosulfate ions, is contained which comprises a complex providing deep color in the electrolytic solution in reaction with the ions of the coloring metallic element 2, such as,'for example, iron, nickel, cobalt, chromium, manganese or copper.
  • the composition of the electrolytic solution for coloring or discoloring is relatively simple.
  • the requirements for the cathode electrode 4 in electrodepositing the elapsed time measuring metallic anode element 1 can be relaxed, so that the electrolyzing current density can be selected in a very wide range of 0.01 to L0 amps/dm.
  • the advantages that can be obtained by using such a complex in the electrolyte solution have been described above.
  • Elapsed time measuring element 1 cadmium Coloring element 2: cobalt
  • Anode supporting element 3 silver-plated nickel wire ii.
  • Cathode metallic element 4 Silver-plated nickel wire.
  • Electrolytic solution Ammonium thiocyanate 5kg Cadmium oxide lkg Water 1 ltr Glazing agent (gelatin): proper Auxochromic agent (acetone): proper iv.
  • Envelope 5 Glass bulb and stem for a midget lamp v.
  • External film 6 Silicone rubber vi.
  • Base 7 Commercial type base for a midget lamp vii.
  • Current density 0.02-1 amps/dm
  • iron, nickel, copper zinc or tin can be used for the elapsed time measuring metallic element 1.
  • the auxochromic agent serves to promote the coloring by the complex and in place of acetone an organic compound with a small molecular weight, such as methanol or ethanol, can be used.
  • auxochromic agent gives a subsidiary action in that it improves the electrolytic effect in the electrolytic solution at a low temperature, because the freezing point of the electrolytic solution can be reduced by addition thereto of the auxochromic agent.
  • the result is that the actual working temperature range for the electrolytic solution can be extended.
  • the coloring metallic element 2 comprises copper, silver, cobalt or iron and it is most favorable that the discoloring agent in the electrolytic solution is salicylic acid or nitroso-R-salt.
  • the discoloring agent in the electrolytic solution is salicylic acid or nitroso-R-salt.
  • zinc, tin or cadmium is preferable, considering that the conditions for the normal electrode potential relative to the electrolytic solution and for the discoloring due to the reaction of the elapsed time measuring metal with the discoloring agent must be taken into account.
  • the color of the electrolytic solution is changed from gold to red by electrolyzing of the coloring metallic element 2.
  • Elapsed time measuring element 1 zinc Coloring element 2: cobalt Anode supporting element 3: gold-plated Dumet wire ii.
  • Cathode metallic element 4 nickel iii. Electrolytic solution Zinc sulfate 250g Magnesium sulfate g Aluminum sulfate 30g Boric acid 20 Water lfitr iv. Discoloring agent: nitroso-R-salt According to the present invention, as described above, a predetermined lapse of time can be recognized with ease only by viewing directly the discolored electrolytic solution in the envelope without any restrictions on the position of the timer in use and with no need of any additional external means such as an external indicator instrument or a display. The manufacturing cost is very low. Therefore, the elapsed time indicator of the present invention is suited for easy use in large numbers to recognize predetermined elapsed times, for example, the maintenance times of electric and/or electronic equipment.
  • remote supervision of the automatic warning in discoloring or coloring can be realized if the present invention is used in connection with external means.
  • an elapsed time indicator including an envelope, an electrolytic solution, an anode electrode and a cathode electrode housed in said envelope, the improvement wherein:
  • said anode electrode comprises an elapsed time measuring metallic element (1) and a coloring metallic element (2) superposed on one another, the normal electrode potential of said coloring metallic element (2) being higher than that of said elapsed time measuring metallic element (1), and lower than the electrolyzing potential of said electrolytic solution, so that electrolysis of said elapsed time measuring metallic element (1) preceeds that of said coloring metallic element (2);
  • said electrolytic solution contains a substance which reacts with said coloring metallic element (2) on electrolysis 6 thereof, so that electrolysis of said coloring metallic element 2) causes the color of said electrolytic solution to change.
  • said envelope contains at least one bubble in said electrolytic solution to inhibit the increase of internal pressure in said envelope.
  • said envelope comprises at least one mass of foamed material in said electrolytic solution to inhibit the increase of internal pressure in said envelope.
  • the indicator of claim 1 comprising a rubber-like material, which is at least semi-transparent, coating the outer surface of said envelope.
  • the indicator of claim 1 wherein said electrolytic solution contains a ligand forming a deep-colored complex in reaction with the coloring metal ions produced by electrolyzing/ said coloring metallic element.
  • said coloring metallic anode element is at least one element selected from the group consisting of iron, nickel, cobalt, chromium, manganese and copper.
  • said elapsed time measuring metallic anode element is at least one element selected from the group consisting ofiron, nickel, copper, zinc, cadmium and tin.
  • said electrolytic solution includes a discoloring agent to discolor or color said electrolytic solution in reaction with the coloring metal ions produced by electrolyzing said coloring metallic element.
  • said coloring metallic anode element is at least one element selected from the group consisting of copper, silver, cobalt and iron.
  • said elapsed time measuring metallic anode element is at least one element selected from the group consisting of zinc, tin and cadmium.
  • said discoloring agent comprises at least one material selected from the group consisting of salicylic acid or nitroso-R-salt.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Measurement Of Unknown Time Intervals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US127193A 1970-03-31 1971-03-23 Elapsed time indicator having color indication Expired - Lifetime US3679976A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2755770A JPS4938188B1 (enrdf_load_stackoverflow) 1970-03-31 1970-03-31
JP9854370A JPS5010750B1 (enrdf_load_stackoverflow) 1970-11-09 1970-11-09

Publications (1)

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US3679976A true US3679976A (en) 1972-07-25

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US127193A Expired - Lifetime US3679976A (en) 1970-03-31 1971-03-23 Elapsed time indicator having color indication

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US (1) US3679976A (enrdf_load_stackoverflow)
DE (1) DE2112793C3 (enrdf_load_stackoverflow)
GB (1) GB1347895A (enrdf_load_stackoverflow)
NL (1) NL7104220A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206838A (en) * 1978-07-28 1980-06-10 Micro-Circuits Company Time-lapse indicator or the like
US4367957A (en) * 1978-07-28 1983-01-11 Micro-Circuits Company Time-lapse indicator or the like
US20090159462A1 (en) * 2007-12-19 2009-06-25 Mettler-Toledo Ag Method of regenerating amperometric sensors

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910647A (en) * 1957-05-31 1959-10-27 Raytheon Co Elapsed time indicators
US3045179A (en) * 1959-09-08 1962-07-17 Henry B Maier Solid state elapsed time indicator

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910647A (en) * 1957-05-31 1959-10-27 Raytheon Co Elapsed time indicators
US3045179A (en) * 1959-09-08 1962-07-17 Henry B Maier Solid state elapsed time indicator

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206838A (en) * 1978-07-28 1980-06-10 Micro-Circuits Company Time-lapse indicator or the like
US4367957A (en) * 1978-07-28 1983-01-11 Micro-Circuits Company Time-lapse indicator or the like
US20090159462A1 (en) * 2007-12-19 2009-06-25 Mettler-Toledo Ag Method of regenerating amperometric sensors

Also Published As

Publication number Publication date
DE2112793C3 (de) 1974-07-11
DE2112793B2 (de) 1973-12-13
GB1347895A (en) 1974-02-27
NL7104220A (enrdf_load_stackoverflow) 1971-10-04
DE2112793A1 (de) 1972-03-23

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