PT103671B - SOLID STATE METER AND CONTROL SYSTEM AND MANUFACTURING PROCESS - Google Patents

Abstract

THE INVENTION IS A SOLID STATE TIME METER WHERE THERE IS PROGRESSIVE CHANGE OF COLOR THROUGHOUT A DISTANCE BASED ON THE PRINCIPLE OF DETECTION AND ACCUMULATION OF LOADS WITH MEMORY EFFECT (EFFECTIVE PERSIST AFTER CLEARING THE ELECTRICAL STIMULUS GOVERNING IT) IN STRUCTURES COM ELECTROCROMIC MATERIALS AND A MARKER ELECTROLYTE THAT LEAD TO A PROGRESSIVE CURRENT INCREASE ASSOCIATED WITH THE DECREASE OF CONDUCTIVITY WITH DISTANCE BETWEEN ELECTRODES TO A MAXIMUM SATURATION VALUE, FROM WHICH THE CURRENT DECREASES ABRUPTELY, ASSOCIATED WITH THE AMENDMENT OF THE OXIDATION STATUS WHEN IT RELATES WITH THE TIME, FUNCTION OF THE RESISTIVITY OF THE MATERIAL AND THE INDUCED REACTIONS INVOLVING CATIÕES, ANIONS AND OTHER IONIC SPECIES, RESPONSIBLE FOR THE CHANGE OF THE OPTICAL PROPERTIES, BEING THE REVERSIBLE EFFECT, BY THE APPLICATION OF AN ELECTRIC STIMULUS OPPOSITE TO THE INITIAL.

Description

description

Solid state measuring device and its control system and manufacturing process

Field of Invention The present invention relates to a new system and process for measuring, and controlling time using a solid state device, wherein the principle of operation and measurement is based on a cumulative process of storing boxes by a static electric field, applied or induced, continuously or discretely and its intersection with itself: means sustaining them, leading to alteration of the oxidation state of an oxide constituting the central part; of the present invention, leading to: a change in its _: physical properties, translated by a progressive color change that is maintained even without any electrical stimulus applied due to the memory effect it has, the function of the accumulated charge and the resistivity of the medium. make up the system of the device, which determine the time interval in which the color change takes place in a dadO; longitudinal or transverse physical space; thus allowing the function or life control of a given equipment, product, component or physical function according to: its field of application.

The device consists of a substrate (rigid or flexible), on which a film of an electrochromic oxide is deposited: and an electrolyte containing a marker element, which is responsible for the color change, which is observed progressively, followed by the placement of two metal electrodes; transverse or longitudinal, depending on the intended operating mode of the solid state meter, that is, the progression of the color change. At the top of the device is the placement of a material as a protective agent, depending on the encapsulation and its field of application.

Summary of the Invention

The invention is a solid state time meter which is based on the principle of charge detection and accumulation in structures with electrochromic materials (chromatic variation with the application of a continuous or induced potential difference) and how oxidation state and thus color, as well as its retention by energy-free memory effect applied after: cessation of the stimulus that originated it, which relates to the time, function of the resistivity of the material, is induced reactions involving cations. , anions and other ionic species present, giving rise to. a change in optical properties, the effect being reversible upon application of one. electrical stimulus opposite to the initial one. The device functionality is not altered when subjected to vibrations, unless the material rupture, which leads to destruction of the ^first distribution, car ga s umu1ada sac.

Background of the Invention k use of time indicators / controllers: in instrumentation, namely in the fields of medicine, electronics, precision industry, food industry, analysis industry, packaging and other products where their usefulness signaling is relevant particularly in devices or systems whose reliability and product quality are directly linked to the lifetime of such equipment, products or components.

In any of these applications the. control system safely informs you that the life of the device or equipment is nearing the end of: life; or safety, thereby making the

even if/ was replaced or working fast cu. on one clear warning to the user that the component, product, article or. equipment fits ontra working out of specifed desired actions or your term of shelf life has expired. In most cases p r et also que: es te indicator life time be low c : this, from consumption c ie negligible energy al robust and dimensions not disturb the space or the equipment where if integrates.

The earliest technology-based time meters, called indachrom, work as an integrator of. amount of charge (electrical current) that flows through and relates to the device. time by displacing a marker that moves on an electrolyte placed in the middle of two columns of mercury. The great disadvantage of this meter is that it uses mercury, is unstable when subjected to vibrations or significant temperature variations, as well as the fragility of the capillary tube supporting the system.

There are currently several time indicators, and here are some documents that address different spoils with this function:

Thus, US4804275 relates to an indicator consisting of a line of electrochromic material, an electrode disposed in a. end of that same line and an electrolyte a. cover the device. After activation (which is performed at temperature), the diffusion of ions and electrces to the electrochromic material is initiated and a change in color thereof occurs. This device does not need a power supply since ¹ is thermally activated This invent although explore elertrccrômicas functionality of a material-oxide, its principle: the detection is different from the present invention: exploits the effect linked to a field induced electrical energy while the previous patent explores the thermochromic effect of materials.

Q KR9309512B refers to a temperature indicator indicating the state of deterioration of frozen foods. This indicator is supported by lecithin, and phospholipase as top and pH indicator. Although it is a time meter, the materials used and associated functionalities have nothing to do with the present event, which uses materials and operating principles different from those mentioned above.

document KR2002054947 of 2002-07-08, inventor EUN_SEY_EONG (KR) refers to a time measuring device in which there is a metal element such as copper performing similar functions of the indachrom device. It is a device that allows tracking a data, system and its synchronization, according to a given reference. Although their operation seems similar to that of the indachron, in which there is also an electrolyte in which the metallic indicator moves, it has nothing to do with it or the object of the present patent, other than that it is not based on the same physical principles of operation. It is neither composed of the same materials, nor can it be considered to be an integral solid state device.

The European patent document, reference numeral EP0223343 A2, refers to a full time meter based on the tetmochromic effect not included in the claims of the present invention.

As it turned out, none of the events described above and other analyzes encompass or correspond to the current patent application.

applications

The main industries: which are potential users of .meters / controllers: of time are:

Medical, aeronautical, mechanical, industry. chemical, environmental, forestry, processing and electronics, for controlling the lifetime of specific components or products in equipment or systems.

- Food Industry, agribusiness industry; beverage and similar industry and the pharmaceutical industry: For quality control of manufactured products in terms of consumers and producers, ensuring that they are. are valid and within: use or operating specifications.

The present invention is intended to replace current mercury-based time meters / controllers while simultaneously meeting current needs such as miniaturization, reliability, accuracy, stability, low cost, and the like. have a sound or light detector that warns the operator that the equipment or device has reached its end of life. In addition, in terms of the food industry, advise the consumer whether the product or component or system they are purchasing is within or will be valid by simple inspection of the indicator attached to the product, component, equipment or system in question. .

The present invention aims to replace the current mercury-based time meters / controllers while simultaneously meeting current needs such as minlaturization, reliability, accuracy, stability, low cost and having a sound or light detector that warns the operator. that the life of a given product, component or equipment has expired and is therefore out of date to be used for consumption, analysis, use in.

equipment where their functions are relevant to the reliability of the results or the health of the products, particularly in the food industry.

General Description of the Invention The present invention relates to a novel, time-based measuring and centering system. solid state device.

The device is composed of a substrate (rigid or flexible) on which a film of an electrotromic oxide such as tungsten oxide and an electrolyte is deposited; using a standard physical, physicochemical or chemical process such as thermal evaporation, sputtering, sol-gel or inkjet printing.

On top of the device is optional the placement of a material as a protective agent, such as lamination or the deposition of a protective film as

fluoretc of magnesium or an oxide high strength chemistry and. mechanics like Si Ox, · SixNy, or using one material polymeric pc type d i vini1 depending of

desired encapsulation.

This event is based on the fact that an electrochromic material changes its optical properties when subjected to a determined potential difference, static, dynamic or instantaneous, when associated with a component or system to which it is aggregated by progressive color change. resulting from the application of _a: voltage of 220 v or 110 v and .24 v or 9 v or 6 v or 1.5 v or another predefined voltage continues flashing cu. instantaneous, no. direction or direction about which you want the progressive color change to take place. The electrocratic materials can be divided into. two classes: inorganic oxides and organic materials. Another classification relates to the potential to which the coloring process occurs [1]. Thus, oxides

and 1 e c t roerom e s (mg materials inorganic) may have cathodic coloring when the state of coloring is 1nduz gone po r ten soe s negative occurring in Ti oxides, Nb, Mo, Ta. and W or n '0 a nbd.ica when the state of co 1 prayer i i nduz i do for positive tensions occurring: in Cr, Mn, Fe, Co, Ni oxides Rh and Ir [21, all of them oxides of: metals: of transition... The redox reaction, for a

inorganic elecfrochromic and given by the following general equations:

(D

Cathodic staining: yG -f- ye + MO, (colorless) <=> AyMOx (colorado),

A '= H ⁺ , Li ⁺ , Na% Aq, (2)

C-Q1 OL OLi 'c c c c c:::::::::::: Gd J yA ”+ yh ⁺ + MO, (colorless) <& A _y MO, (colorado), (3)

A ”= F ' _f CN \ OIT; 0 <v <0.3. (4) where the letter M se refers to the metallic species present., And to the eyex oxygen at _: .respective: molar percentages present in the reaction leading to the color change.

In addition to: inorganic materials, we must also consider organic materials, namely materials that do not. Over the last decade, they have been found to exhibit exceptional electrochromic properties such as vialogens, which have a very attractive feature in which they can acquire different colors as different substituents are introduced into their molecules.

Polymeric electrochromes, also belonging to this class, have some advantages compared to other electrochromic materials. The production and development costs of these polymers are generally lower than relatively inorganic electrochromic ones which are normally deposited by processes to healthy film materials such as electron gun assisted thermal evaporation or magnetron-assisted cathodic puiveresis, or epitaxial or molecular molecular weight. By decomposition by a radio plasma possible ¹ different colors depending on the activating elements: or stabilizers added to the polyrum, also constitute a great advantage over the other existing electrochromics. An example of this type of material (multicolour electrochromy) is polyaniline which with successive increase of the anodic potential, the transparent film changes to green, blue and purple. most are chemically unstable and have a high sensitivity to UV radiation, which is the main reason for the shortened lifetime of: a device in an application was outside (outside doors).

The production process of the materials: described above is based on: chemical, physical or physicochemical techniques, such as chemical vapor decomposition (Ç V.D Chemical Vapor Deposition} [1,4]; rf plasma assisted chemical decomposition of vapors (PECVD, see Figure 4), pulsed laser [5]; sol-gel [6-3]; immersion techniques; atomized pyrolysis [3]; direct current or radio frequency sputtering [6,10,11]; with or without the presence of a magnetron, thermal evaporation by heated filament or electron gun [6] and electrochemical growth [6,12].

The subject solid state time measuring devices of the present invention require, in addition to the electrochromic material, the incorporation of a material called a marker (electrolyte or ion conductor). This material, through the movement of the phonic species that pass through the electrochromic material, will modify its optical density (coloration). So we have: que ::

yA ⁺ + y + Mcp (colorless) o A _Y M: 0 _K : (colorless) (5) where A = d ', Li ⁺ , Na. (6)

In terms of the operation of the solid state meter, one parameter: important is the coloring efficiency IC1, expressed in ente ' ¹ , which determines the optical behavior of electrochromic materials as a function of the stimulus. electric field <To. The determination of this parameter, total injected / extracted loads per unit area as well as the optimal density (Scd) must be known.

The resulting load density is calculated as:

S _QC = log (T ₃ (Δ) / 'T _C (X)) where T ₀ represents the initial transmittance

T ₀ :, at ransmitã c ia after staining., For a given wavelength λ.

Ά staining efficiency is determined by the following equation:

EC (l) = §O: D (M / Q, where Q translates the transferred yoke [1,6]

In addition to the electrochromic material and the marker, it is an integral part of the solid stay meter one. _f electrolyte material may be liquid electróliws _f solids, inorganic or organic electrolytes eleedrolitos as paiimêricos.

In the particular case of liquid electrolytes, usually based on strong acids or strong bases, which has the major disadvantage of the possibility of leakage of the liquid material to the outside of the device as it requires a holding container, usually made of glassy material. or palmeric which must be conveniently sealed. Cs more liquid electrolytes. · · are: sulfuric acid (HgSCU), hydrochloric acid (HCl). <1> nitric acid (HNQ3À and the LiClcl [lithium perchlorate) solution with PC (propylene carbonate] in concentrations ranging from 0.01 moi / dm * at 10 mol / ctat using

demonstration us te case 10 mol / dir ¹ , For: el .eotrolytes sol Inorganic acids: ices, euistem several, I am the more used > no convenient s to the present event are: c ) l ₃ n, ly LEL, LiNbCb, in the form this is equiometric or not, face to.s excellent Features penetration and mobility the sociudas

lithium

Polymeric electrolytes are characterized by having as base or matrix one or more polymers. Of the most widely used and studied salts in this type of electrolytes are LiCICu, Li, LiBr, LiAsFg and LIcF3SO3, in stoichiometric or do not. The great advantage of this type of electrolytes is a. possibility of being autonomous also, as encapsulating agent.

Regarding the conductivity to. the. For the different types of electrolytes described above, there may be variations between 0 ', 33 d / cm (for liquid electrolytes) to 10 ~ ^T: S / cm' for inorganic and polymeric solid electrolytes [6], which will condition this. the response time and therefore the process of progressive color change associated with a given physical space, transverse or longitudinally.

As described above, the device may be developed in different substrate types such as glass, polymer and paper. Materials used as a support or substrate may be

or non-transparent device. depending on of the application of In accordance with the described ante ri orment and the device will have two electric metallic or c ompor t amen t me 1 a cc, that allow the application or electr field induction static and the control of loads if necessary. constituted s by materials metallic conductors such as chromium, you so, silver, aluminum, gold and Other make up: 3tos based on

enumerated elements as well as conductive oxides

transparent from high conductivity, as for example 1, oxide alloys of. Indium and zinc .. In accordance: as described previously, c

The device may or may not be encapsulated using glassy or polymeric materials, such as by gluing or laminating. The materials used as a backing or substrate may or may not be transparent depending on the application of the device.

Detailed Description of the Invention

As noted above the present invention relates to a novel system and process for measuring and controlling time.

solid state device (see Figures 1 to 31 is a film of an electrochromic oxide (produced on a rigid or flexible support; upon which it is deposited; an electrolyte containing the marker element which reacts with the electrochromic material). change 4is observed color 'in juxtaposed or layered form depending on the mode of operation of the device, transverse asymmetrical variation of the color: or longitudinal variation of the color. At the ends of the device (see Figure 3) are placed electrodes which when connected: a battery to allow the diffusion of Li ions ^T (label): polirtórico from the electrolyte salt for electrocrómioo _Material:. Ά diffusion of lithium ions depends on the structure and morphology of stoichiometry ,, electrochromic material [4] the front is associated with the movement of the marker and is started at the anode (terminal connected to a positive potential) and its progression The faster the voltage applied along a graduated scale is not faster. In this context, the lithium serves as an indicator of the direction of the change progression: of color, qualitatively graded: in units of time per unit of space, such as hours per millimeter or months per millimeter, translated by A continuous increase in current As the color progresses over a distance, as indicated (32) to a saturation limit value (33) to which: a sharp change in the coridutivida.de, which increases, corresponding to a sharp decrease current that the device supplies.

In addition, once the applied voltage is removed the device retains the color along the graduated scale, thus having the ability to retain given information ie memory.

In accordance with previously described, the measurement process is reversible, i.e. ₇ changing the direction of the polarity of the voltage applied electmcrómico material reacts in the opposite direction, a very small ccm response time · :, returning to have conductivity and therefore the initial color without applying any tension. That is, all recorded measurement information is erased. _:

Device Development

For © processing of a measuring device / time controller it is possible to use different materials ¹ electrocrómiccs so eating electrolytes, but it is noted, as an example, a particular case of the device: designed on a glass substrate, comprising tungsten trioxide ( WO3) there is a stoichiometric form or not and a polymer electrolyte.

1. Substrate Preparation

The glass used as a substrate is subjected to a process of. cleaning. Initially isopropílicQ is dipped in alcohol at temperatures ranging between 30 ° ^ C and 50 ° C being chosen for this exempl.0 ¹ to 50 ° C in an ultrasound for a period of 15 minutes. After this time the substrate is withdrawn from alcohol and immersed in ultra-pure water at temperatures between 4D ^Q · C ⁹ and C 50 S5 for a period equal to anteriorv Subsequently, the substrate is dried with a jet of nitrogen.

2. Deposition of electrochromic material (WO _Xf 0 <x <3)

The ^first trróxido · tungsten is deposited on a glass substrate (10 x 10 cm) by physical deposition technique such as resistive thermal evaporation (Figure _4): by electron guns (Figure 5), sputtering (figure 6) · ura or chemical process, such as inkjet printing (figure 7) or sol-gel, at temperatures ranging between 20 ° C and 35 ⁰ C '. In the case of: physical techniques, the growth rates of the films can be very high, exceeding 3 nm / s, and the process costs low, particularly in the case of thermal evaporation, when compared with other deposition techniques: such as electron gun assisted thermal evaporation or sputtering.

3. Preparation of polymeric electrolyte

Within a controlled atmosphere glove chamber, a highly sensitive material to the charge accumulation process is dissolved, such as propylene carbonate (PC) solution K, previously dried titanium perchlorate (LiClOu), which acts as a timekeeping element on the solid state meter.

In parallel, the organic material that will function with the solid state meter electrolyte material such as polymethyl methacrylate (PMMe) in ethyl acetate in a ratio of 1: 5 to 1:10 is dissolved. Finally a. The above solution is mixed in LiClCg + FC [1 M] in a ratio of 2: 5 to 2:10 to incorporate the label in the electrolyte.

4. Production of the substrate device: glass or polymeric, with the deposited electrochromic oxide film: it is cut according to. the desired maximum boundary geometry and progression time for a given application, such as for d. 2,9 cm in length, (distance from which the color change will take place: of color: a total space of about 2, without, discounting about 0,4 cm, for metallic contact and encapsulation; and 0,2 cm of: width Then a layer of rich electrolyte is spread over

The desired final device is then placed in an oven at 60 ° C for evaporation of the solvent of the electrolyte, followed by com. the transverse or longitudinal space and a

CTO L: OHIC Metallic ohmic, which contacts e 1 e ct r o c om er with polymeric electrolyte, consisting of material other than aluminum, <:

Omium, gold or silver titanium, produced by a technique similar to that used for the production of electrochromic material, such as resistive thermal evaporation.

Placement of a glass or other transparent inorganic or organic material on top of the device after electrolysis for encapsulation is optional, but corresponds to the process of sealing and protecting the device to make it function independently of the device. conditions: environmental conditions you are in. This encapsulation operation may be performed by any technique known in product assembly processes, such as lamination (see Figure 51).

Figure 8 is a graph of the current: (A) as a function of time (hl, for a time meter / controller tested: with an applied voltage of: 6V. The device at the end of the scale (corresponding to a sweep of 2.5 cm) the value of the electric current flowing through it decreases abruptly as it reaches its lifetime (maximum spatial color, transverse or longitudinally according to the desired time meter structure), It is therefore possible to couple an audible / light alarm signal to this device as an end-of-life indicator.

Description of the figures

Figure 1 - Represents a possible configuration of the electrochromic time meter / controller device according to. the subtitle.

1— Substrate (rigid or flexible material, such as glass or polymer or paper).

2- Metallic contacts, through which · se. make: connection to outer electrical circuit .:

3- Material is 1 ect r o c r om i.eo 4- material electrolyte: 5- scale indicative of variation ^ progressii is the color between the two metal contacts.

Figure 2- Schematic solid explosion indicating:

^ Z How to do it:

CL progressive variation of corde with a.

subtitle.

- mode indication as if process the change ck ^: i coloring, cyclic view '> side of electrolyte from of metallic contact.

Figure 3 - Schematic of the solid state meter shown in figure 1 but with the metallic counts located at the laterals, indicating the polarization form: and highlighting the encapsulation, on both sides of the device, according to the legend of the figure.

7- Encapsulating material (eg glass, polymer or a high resistivity oxide).

3- Continuous polarization source.

Figure 4 - Representation schematic of a system of film production by thermal evaporation resistive, showing details from camera wrath according to caption of figure. 9- Substrate or target port 10- Substrate, on the which one do you want c ieposition the device 11- Interior of the chamber in depression of order of Irmo ' ⁷ It may or may not contain an inert gas with k> the Argon.

12- Evaporating material flow.

13- Chamber of Process.

14- Heat resistance / Crucible containing the material to evaporate.

15- Intake of gases (oxygen, argon, hydrogen, nitrogen, ...) into the chamber.

16- Exit to the chamber evacuation system.

17- Source of. power, W) of the crucible containing the material to evaporate

Figure .5 - Schematic of a source: of thermal evaporation by electron gun, showing; the details of the electron gun, according to the legend of the figure.

18- Crucible containing the. material <to evaporate

19- Focusing the electron beam.

20- Electron gun (source of electron production :).

21- Crucible / oven water cooling system.

IS

Figure 6 - Generic schematic of a sputtering process according to the figure legend.

22- Electrode to which the continuous or alternating radio frequency energy signal containing the target is applied (cathode /, which may be laterally rotated by a magnetic field).

Reactive gas injector, such as oxygen, located near the target and consisting of non-conductive material.

24- Ionized gas species, such as argon,

Figure 7- Ink cattle print film production system, where its components are in accordance with the legend.

25- d input It's injection the gas inert in order to push the solution chemical bread a towards the atomizer, 26- atomizer. 27- Nano Drops la solution timeless. 2S- housing ¹ / container of the system inkjet, which

It contains a particle atomizer, the chemical solution to be sprayed in a controlled manner on a substrate, and the heating system.

29- Heating / polarization resistance.

Figure 8 - Graphical representation of current as a function of time for a time meter / controller tested according to the legend in the figure.

30- Ordinate of the graph, which represents the variation of current in amps (A) and where each division corresponds to 0.5x10 A.

31. The abscissa of the graph that represents the variation of time in hours (h) and where each division corresponds to 1 h,

32- Current variation curve over time for an applied voltage of 6 V

3.3- Indication of the condition of. meter corresponding to the color change to the opposite metallic electrode and corresponding to an abrupt change in current.

34- scale indicating the direction of progressive color variation over a space of 2.5 cm.

Bibliography [1] K., Bangé, Colburation of tungsten oxide films: A model for optically active coatings, Solar Energy Materials & Solar Celis 58, 1-131, 1999.

[2] C. fig. Granqvist et al, Recent advances in elcctrochromics for smart windows applications. Solar Energy 63, 199-216, 1998.

[3] R, Gorden, S. Barry, J. Barton, R. Broomhall-Billard, Atmospheric Pressure Chemical Vapor Deposition of Electrochromic Tungsten Oxide Films, Thin Solid Films, 392, 231-235, 2001.

[4] D. Gogova, A. lossifova, T. Ivanova, 2, Dimitrova, K. Gesheva, Elctrochromic behavior in GVD grow tungsten oxide films, Journal of Crystal Growth, 198/199, 12.30-1234, 1999.

[5] G. Fang, K. Yao., Z ... Liu, Fabrication and electrocnromic properties of double layer

WCç (V) / V _Z O _S (Ti) thin films prepared by pulsed laser ablation technique, Thin Selid Films, 394, 64-71,

2001

[6] CG Granqvist, Hand bool of inorganic electrochromic materials, Elsetier, Amsterdam, 2002 [7] S. Eadilescu, P.shirt, Study of nanostructured sol-gel prepared WO3 Thin films and composites for electrochromic applications, Solid State Tonics, 8830 , 1-11, 2002.

[8] M. Hashizume, 1. Kunitake, Ptepartion and functionalization of self-supporting (polymer / metal oxide) composite ultrathin film., RIREM Review, no. 38; Focused on Nanotechnology in RIKEN II, 2001.

[3] M. Regragui et al, Electrochromic effect in W ₃ , thin films prepared by spray pyrolysis, Solar Energy Materials & Solar Cells, 77, 341-350, 2003.

[1,0], d .. Scariiiinlo, Tensions electrooromic and mechanical effects observed in photochromics in tungsten oxide films. Brazilian Journal of Vacuum Applications, 2: 0, 52-57, 2001 ..

[11] S. Lee, H. Cheong, J. Zhang, A. Mascarenhas, D. Benson, S, Deb Electrocliromic mechanism in the _{Y-W0 3} ._ thin films, Applied Physics Letters, Vol. 74 n. ^Q 2,

. 242-244, 1999. [12] HW Heuer et al Electrechrcmic window based on conducting PEDT / PS3, Advanced Functional Materials, n, 2, 92, 2,002:., ..

[4] S. Papaefthimiou, G. Leitheriotis, P. Yianoulis, Fudy of Films with Textured Surfaces for Improved Electrotiiromic Performance, Solid State Lonics, 139, 135-144, 2001.

Monte da Caparica ,. .1.6 February 2007

Claims (11)

Claims 1. A solid state time measuring device comprising a structure composed of a rigid or flexible substrate 111, such as glass or fflylar or plasticised cardboard or paper, followed by the insertion in layers or top-to-bottom juxtaposition of the following: films: a film of an inorganic electrochromic oxide (3) such as tungsten oxide in stoichiometric or non-stoichiometric form with Xxii, or organic such as polyaniline and one; electrolyte (; 4) which may be a polymeric solid: with a dissolved label such as 11thio, such as LiClOx 0 <x <4, or Lil, or O LiBr, or 0 LiAsFg ·, or O LiCFaSÇg, in the forms stoichiometric and not stoichiometric either. an inorganic material such as Li _K N (0 <x <3) or LiALF 3 or LiNbO ₃ in stoichiometric and non-stoichiometric forms or a liquid electrolyte such as sulfuric acid [HzSQd _f hydrochloric acid (HCl) means nitric acid (HNO3) in which the titanium marker is dissolved or a liquid solution which already contains it as · Li.ClCh (lithium perchlorate; PC (propylene carbonate) solution in varying concentrations of 0.01 mol / dm ³ to 10 mol / dm ³ , all with conductivities of at least 10 ” ^3: S.çrtT ¹ altered by accumulation of electric loops, followed by the placement of two metal electrodes (2), including there is a custom scale: and is encapsulated using an inorganic or organic material (7) A solid state time measuring device according to claim 1, characterized in that the inorganic electrochromic oxide may be constituted by 1/4 by any oxide containing a transition metal such as Ti, Nb., Mo, Ta and W or alternatively Cr, Mn, Fe, Co, Ni Rh and Ir. A solid state time measuring device according to claim 1, characterized in that the electrochromic material used is an organic material such as vialogenic materials such as polyaniline. 4 :. A solid state time meter according to claim 1, characterized in that the electrolyte containing the ionic marker is an inorganic material such as Li _Z N (0 <x <3) LiALF _y 0 <y <4), LiNbC _z 0 <2 <4, with conductivity lower than ICG S / cm. A solid state time meter according to claim 1, characterized in that the electrolyte containing the ionic marker is an organic material! such. such as L.iCl; O _x Q <x <4, Lil, LiBz, .LlA.sF _s and hiCFsSOs, in stoichiometric or non-stoichiometric form, with conductivities below 1.0 ° · ° S / cm. A solid state time meter according to claim 1, characterized in that the electrolyte containing the ionic marker is an acidic aqueous solution containing sulfonic acid (H. ₂ S'Cç), or hydrochloric acid (HCl), or acid. nitric nitric oxide) or a solution of Licicp (lithium perchlorate) with propylene carbonate (>C> in concentrations which may be from W mol / dm ³ to 0,01 Mol / dm ^J with conductivity equal to or greater than 0,0033 S / cm, A solid state time gauge device according to claim 1, characterized in that it has a capping layer comprised of magnesium fluoride or a high chemical and mechanical resistance oxide such as SiO _x , MA.cu using a material. polyvinyl type polymer. Solid state device: A time meter according to claim 1, characterized in that it contains a marker, such as lithium, which promotes color shift in front of a qualitatively graded scale in time units per unit. , of space, such as hours per millimeter or months per millimeter, translated by a continuous increase of current as color progresses over a distance as indicated (32) to ^: a saturation limit value (33 ). 9. Solid state measuring method of manufacturing the car-by-acteriza -depositadas all layers on the substrate and forming device as mentioned in: the .reivindicações _1: 7 is produced by jet printing: ink. 10. Time measurement process using the device. claim 1 characterized in that the measurement is proportional to the time that a given electrical voltage applied between the vertical or longitudinal electrodes (2) remains, being determined by the asymmetric color change that progresses proportionally to the time on a graduated scale and remains unchanged. after turning off the voltage. Time measurement method according to claim 1, characterized in that the measurement process is reversible, that is, changing the polarity direction of the voltage erases all stored measurement information. Time measurement method according to the preceding claim, characterized in that it provides qualitative information on the time of use of a product, component or system to which it is aggregated by progressive color change resulting from the application of a voltage of 22.0 V or 110 V or 2 V or 9 V or 6 V or 1.5 V or other predefined voltage, flashing or instantaneous, in the direction or direction you wish to change: colored progressive.