MXPA98008798A - Element for the identification of articu - Google Patents

Abstract

A method is provided for the immediate identification of an article, such as a vehicle. The article has incorporated within it, within its coating, two or more substances detectable by X-ray spectroscopy, and these constitute a kind of bar code that can be read by a spectrometer, both qualitatively and quantitatively. Other spectrographic methods can be used, such as the Magnetic Resonance-Nuclear (NMR) spectrum, neutron energy dispersive spectrum (NEDS), and electron rotation resonance.

Description

ELEMENT FOR THE IDENTIFICATION OF ITEMS FIELD OF THE INVENTION This invention relates to elements for the identification of articles and a means to identify vehicles, television sets and other items subject to possible thefts is particularly useful.

BACKGROUND OF THE INVENTION The incidence of thefts of motor vehicles and domestic appliances continues to grow despite the introduction of novel and ingenious devices. These devices are commonly known as integrated or passive electronic tags or radio frequency (RF) chips, which, by their nature, can be detected, provided information and located. Since today's organized crime syndicates have better scientific resources, it is very likely that part of their action in committing the crime is the removal and destruction of such devices or electronic units, built on their boundaries. The average disassembly of a motor vehicle in its main components, from the moment of its theft, takes a short time and can be done while it is being transported. At the same time, the electronic tracking device can be discarded. The components of such a vehicle can then appear on the market of used spare parts and, reliably by possible non-criminal buyers or legal enforcement.

THE INVENTION According to the invention, a method of identifying an article includes the steps of: introducing or incorporating at least two detectable substances, which have characteristic spectra that can be identified and / or quantified, according to their chemical nature and / or their ratios and / or relative concentrations, by suitable spectrographic elements, in a articles a material, by coating this article, in a predetermined ratio and / or concentration. In this specification, the term "spectrographic element" is used in its broadest scientific sense and includes such techniques as spectroscopy, X-ray spectra, Nuclear Magnetic Resonance, Molecular Spectroscopy and Neutron Energy Dispersive Spectroscopy (NEDS), and electron spin resonance, the first two techniques are preferred for the following reasons: X-ray spectroscopy allows to identify the spectral lines K, L and greater than each element in the periodic system. Their relative intensities give a very precise and reproducible pattern of their relative concentrations.

This is the most versatile method of coding a chemical label on any substance or any material and can be reliably supplied with a device in visible contact with the object in question. A preferred form of X-ray spectroscopy uses continuous waves or pulsed X-rays, which can be made monochromatic by the use of secondary objectives and filter assemblies. These allow an optical form of the quantitative resolution by the synchronous time variation of the energy and the intensity of the X-ray beam produced, allowing to fine-tune the optimal response of the substance or mixture of substances. Alternatively, by regular release, the pulse variation of the energy interval of the spectrum produced from the primary X-ray objective explores the maximum excitation energies and the maximum characteristic resolution of each element to be identified with each pulse or launching. It has been found that the use of X-ray spectra produced by suitable energy sources, as described in my patent application, also pending, No., is very simple and accurate and is the preferred form of spectroscopy. Optical spectroscopy is advantageous for the identification of alkaline or alkaline earth metals, because they have very different optical spectra in the spectrum of the visible or almost visible range. The spectra can be produced quantitatively by a good light spectrometer. For the purpose of defining forensic evidence, the use of molecular compounds, which are not readily available on the market, is preferred, and they can be easily modified by binding to them elements, which are then identifiable by one or a combination of the spectroscopic methods described above. One of the possible candidates for such molecules are the Buckminsterfullerenes or species CgQf c70 '76' c82 and older molecules of the carbon cage. The elements can be attached to their surface or they can be trapped inside. They have different UV and IR spectra and, labeled with other elements, they can be very versatile in the coding process of a chemical label using X-ray fluorescence, or energy dispersive scattering spectroscopy or energy dispersive X-ray activated energy spectroscopy. beams of electrons. Another group of candidates includes metal-organic soaps. In a particular form of the invention, it is proposed to incorporate a sequence of different elements with distinct spectral lines distinctly at distinct and precise known concentrations in any host material or to incorporate the sequence into an appropriate coating for an article in question. The nuclear charges of the elements used can determine the order of reading of the different spectral lines, the intensities of which can determine the value of such reading. For example, the routine of establishing a numerical sequence by chemical labeling can be: Stage 1: Selection of a sequence of elements, for example, Na, K, Rb, Cs, Mg, Ca, Sr, Ba or the lanthanides, some of which can be incorporated. Step 2: Selection of a second sequence of elements, different from the first sequence, for example Ti, Mn, Co, Cu, Zn, etc. , one of which will be incorporated.

Stage 3: Definition of the permutation of the sequence of elements, assigning a permutation of the sequence, shown in stage 1, by the relation of this permutation to the presence of an element of stage 2.

Step 4: Normalize (by definition) the peak length of the element's concentration from stage 2 to a number between 1 and 10, depending on the type of the item producer. These can be permuted similarly to stages 1 Stage 5: Incorporate concentrations of the elements of stage 1, which produce peak lengths between 0 and 10, relative to the concentration of the element of stage 4.

The decoding process seems similar correspondingly. Stage A: First determine the presence of an element of stage 2 and define the normalization of its concentration, according to stage 4. All peaks have to match this normalization and may not exceed 10 in relation to the peak of normalization of otherwise I will be evidence of violation with relative concentrations.

Stage B: define the permutations according to the element in stage 2. Stage C: determine the sequence and concentrations of the elements defined in stage 1.

Stage D: Coinciding with the normalization of the concentration of a combination of elements or elements selected from stage 2. Stage E: Result: Read a sequence of digits that individually label the article or component in question (ID number). This is exemplified with reference to Figures 1 and 2 wherein the coating type paints and burned type coatings and engine oil can be chemically labeled by the mixture of the aforementioned coder elements, provided that the chemical reactivity and The spectrum properties are determined during its production and the coating process. The respective concentrations and coding procedures, which include processes outside the broadcast, are stored in a central computer, so that the sending agent does not know the normalization element and its normalization value. The individual mixtures are then mixed with the host coating and applied to the article in question. An individual ID number, identical or a number corresponding to the stored number is attached to the item by a conventional label or certificate. The homogeneous or superficial labeling of the uncoated articles or components, can be done by internal diffusion or direct mixing, while creating the article. Figure 3 illustrates the internal diffusion profiles of different elements. The reading or reporting devices will be able to supply the producer's name information, which will be transmitted to the central computer unit. The spectroscope element will match the spectrum of the producer to the ID of the producer, which will then adjust the normalization byte in the reading device to a number that determines the normalization of the resting spectrum, which is then transformed into the ID number of the Article. This number is then transmitted to the central computer unit, which faces this ID with any stolen or lost item registered in its database. The central computer unit then sends a signal to the reading device on the site, if the item is stolen, lost. In the event that such registration is not available, the ID number or similar of the correct owner can be displayed for manual correspondence on the site. The investigations so far have given positive results for the mixture of alkaline-type compounds and halogen-type compounds in organic coatings. The solubilities of these mixtures must be taken into account for the normalization process of the coding. It has been shown that chemical coding, as described above, it is possible and that reproducible results can be achieved quantitatively. This is illustrated in Figure 4. The dose method and mixing techniques should be automated by the use of precision distributing machinery, on-site spectroscopy if possible, test sampling otherwise does the work and testing solubility have to be made for all possible candidates for substances in mixture. With the correct precision of the distribution technique, the reading technique is capable of producing up to three digits per element used as a mixture (see Figure 4). This means that if one uses 8 elements plus a normalization or composite element, one can produce sequences of up to 1,000 values in 40,320 permutations as 24-digit ID numbers. However, it is preferred to operate between 3 and 100 different intensity levels to avoid overlaps and fluctuations and measurement errors. In this aspect, the reference to Figure 1 will show by definition certain forgotten gaps related to the intensities that do not correspond to the real numbers. A distributor and mixer unit is supplied using commercially available components. Clear coatings, commercially available, for vehicles are the first objective in impregnating with chemical labeling substances. These will be discussed later. An example of the invention is described below with reference to the accompanying drawings.

Figure 1 is a graph of the Intensity against Nuclear Load, shown for an objective that has four elements A, B, C and D, the ridges are indicated for them. A ridge is also indicated for a G element (calibrator). A scale of the Intensities is shown as a NORM and the lines indicate the relative concentrations. Thus, the crest in A only interrupts the zero line so that the key given for it is zero. The two crests for element B are in 3 and 1, all C is in 5 and D is zero. Thus, the key to this particular objective is G 0 3 1 5 0. In Figure 2, there is a system for creating a key with reference to element G. Figure 3 indicates the depth of internal diffusion of elements A, B and C, on the surface on which they are applied. A typical graph is shown in Figure 4, with the following final analysis giving a key based on iron, which is the calibrator element chosen to represent the 9, which is calibrated by means of the maximum resolution of the hardware (equipment). , rather than the software (program). For use as chemical labels for motor vehicles, the ions of indicator elements in the phosphating suspension, for example an ion assembly with a concentration of 11 variable relative to each other, replacing part of the Zn ions, usually used in the phosphate process. If a dip bath is used, such a combination of ions can represent the year, month and lot number of the vehicles. If the labeling phosphate solution is sprayed on the body work after the immersion bath, individual keys can be made for the bodies of vehicles. The advantage of such treatment of the metal surface is difficult to remove, such a label covers the entire surface of the body work without painting, even very difficult to reach parts. The vehicle or other item can be completely disassembled, the paint completely removed and the body of the metal treated with acid. Then a complete re-phosphating and re-painting will take place, with the risk of remaining remnants of the original chemical label. Such a procedure is not considered in any way viable for criminals. Since the indicator ions can be washed and separated in the rinsing process, after phosphating and labeling, they can not be reused for subsequent labeling, since they will falsify any other label. If there is a closed-cycle water rinse apparatus, the water has to be demineralized after 12 each vehicle to avoid falsification of the label added to the label of the batch applied in the immersion bath. A recovery of the amounts of lost indicators can be expensive. As an alternative, a year / month / batch key can be carried out in the base coat of the vehicles, so part of the total label is difficult to remove, if the paint separates. In this case, several methods of incorporating reactive indicators are possible. For base and paint coatings, the incorporation of indicator ions combinations can be achieved by the addition to the thinning solution of the paint. As a first method, indicator acetate hexahydrates have been successfully transferred into diols (used in, for example, polyurethane paints) of aqueous solutions using organic / aqueous two-phase systems, which have partial solubility from each other. By a distillation process, the water can be removed so that a maximum of less than 1 mol% remains. The organometallic compound forms the organic phase with the indicators. Gas chromatography measurements have shown water contents as low as 0.7 mol% in the organometallic compound solution, which can be used as a drying component in the paint. 13 A second route for safer incorporation of indicators in paint is the reactive incorporation of the chemical label into the key soaps of the indicator. With a solubility of 1 g of label in 10 ml of butanol, this method is very suitable for the process. The amount of metallic soap used in compatible paints, where part of it will be replaced by the indicator label, can be determined by trial and error. An excellent path to incorporate indicator labels resides in the treatment of the cooling system of the engine with a phosphating suspension, followed by the application of the agent that prevents corrosion, then the application of the indicator label solution in the first cooling water supplied in a junction plant. As an additional label, the engine can be sprayed with a colorless lacquer that marks with fire, which contains a combination of indicator concentrati The incorporation of indicators in the engine block during the molding process is an excellent method. The above methods can be applied to differentials, gearboxes, transmission braking system and hydraulic sand systems. 14 The seats, boards and other interior parts made of plastic, fabric or leather, can be treated by the direct incorporation of indicator labels with an impregnation liquid. USE OF LANTANIDES AS DETECTABLE SUBSTANCES For the identification of products, a key can be obtained using the salts of lanthanides, which are detected by XRF. The lanthanides have the following physical and chemical properties.

TABLE I Symbol MR Valencias Potential Electric Index Merck La 138,9055 3 2.52 (cale.) 5193 Pr 140.9077 3, 4 2.47 (cale.) 7605 Nd 144.24 (2?) 3 (4?) 2.44 (cale.) 6295 Gd 157.25 3 - 2.4 (cale.) 4200 Dy 162.50 3 N / A 3467 Yb 173.04 2, 3 N / A 9916 A method of attaching an identification key to any article (car, domestic article or similar) is by the incorporation of the chemical marker in the passivation coating of the metal (phosphate layer) or inside the painting. For the phosphating process, ions for identification can be used instead of zinc. The typical concentration of a phosphate dip bath is in accordance with Ullmann's treatise, Vol. A16, page 412 ZT? ++ 1. 2 g / 1, Ni ++ 0.1 g / 1, H3P0 + H2P04 15 g / 1 and N02 0.1 g / 1. The pH is adjusted to 3.2 with sodium hydroxide. The process is usually carried out at a temperature of up to 952C. The following chemicals were used: Xn (OH) - 1.83 g / 1 NiS0 - 0.265 g / 1 H3PO4 15 g / 1 and NaN02 0.233 g. For the test, the transfer rate of the lanthanides one adds the salts to the phosphating bath and measures the concentration in the XRF layer. To carry out this process in a car production plant, the phosphate solution has to be sprayed after the car is immersed in the phosphate bath. The advantage of this system is the direct treatment of the metal surface and the difficulty in removing the labeling substances from a stolen car. The phosphating solution can not be reused due to the possible leaching of the lanthanides, and in a closed water process, the rinse water has to be demineralized to avoid falsification of the aggregate number. 16 Ions can be added to the thinner or to a portion of the paint (for example, diols in a polyurethane paint). Different solvents have been tested in the solubility of lanthanide acetates at 202c. The salt is added and the solution is heated to boiling. The measurement after cooling showed that the acetate hexahydrates have a molecular weight between 316.04 and 422.24 g / mol.

TABLE 2 Solub Solub max (g / D Water 50 Ethanol 5 Ethyl acetate 0 Butyl acetate 0 1, 3-butanediol 0 n-butane1 0 acetylacetone 0 Further tests were carried out to transfer the ions in an organic solvent. To transfer ions in acetylacetone the salt was dissolved in water and about 2 to 4 times the volume of acetylacetone was added to this saturated solution. A part of acetylacetone 17 was dissolved in approximately 8 parts of water. The rest formed a two-phase system. The denser water is separated to the bottom and the acetylacetone can decant, forming an organometallic compound with a lower solubility than in water. It was used as a dryer in paints. The compatibility has to be checked with the paint manufacturer. To dissolve salts in butanol, one also has to transfer them from an aqueous solution. The polarity of butanol is too low to break the ion grid. A saturated aqueous solution is mixed with about 7 to 10 times the butanol volume. After shaking continuously for about 1 minute, the separation of the two phases disappeared and a homogeneous phase formed. The water can then be separated by distillation. This is preferably done under a vacuum below 200 mbar. The steam is an azeotrope with around 80% molar of water, after distillation of 3 to 4 times the volume of water added can be brought below 1% molar. The end of the distillation can be seen by an increase in steam temperature (at 1013 bar) from 92 to 118SC. Preferably the chlorides should be used since they have the highest solubility. 18 The water content of the butanol-water distillate was measured with the HP 5890 series II gas chromatograph, using a TDC detector. Sample I was taken after 2 hours of distillation in a small distiller with a primary content of 50 ml. The pressure was of 173 mbar and the average flow of the condensed vapor was about 10 ml / h. Sample II was subjected to an additional one hour distillation, after which the area ratio was 0.0076. Sample III was a sample calibrated with 1 mol% of water in n-butanol. The area ratio was 0.021. Result: it was established that distillation leads to water contents well below 1% molar. Another very promising way to incorporate the salts in a paint is to react them in a metallic soap, which must react with the butyric acid. After evaporation of the excess of butyric acid to 18ose, a gelatinous precipitate is obtained. The product of 1 g of neodymium acetate is dissolved in 10 ml of butanol for about 6 hours. After that time, it begins to recrystallize slowly. 19

Claims (10)

1. A method for the identification of an article, which includes the steps of introducing or incorporating at least two detectable substances, which have characteristic spectra, which can be identified and / or quantified, according to their chemical nature and / or their Relative relations and / or concentrations, by suitable spectrographic means, in an article or a material for coating the article, in a predetermined relationship and / or concentration.

2. The method, according to claim 1, wherein the identifiable spectrum is the X-ray spectrum.

3. The method, according to claim 2, wherein the X-ray spectroscopy, allows the identification of K, L and the upper spectral lines of any element.

4. The method, according to claim 2 or 3, wherein the pulsed X-rays are used, which are made monochromatic by the use of lenses and secondary filter assemblies. twenty

5. The method, according to claim 2 or 3, in which the pulsed X-rays are derived by varying the excitation of a primary target, these pulsed X-rays are used to track in the complete response functions of each present element, through of the maximum of its resolution functions.

6. The method according to any of the preceding claims, wherein the detectable substances are chosen from the Buckmínsterfullerenes or species CgQ c70 'c76' c82 'and higher species of molecules of carbon cages, with one or more elements there united.

7. The method according to any of claims 1 to 6, wherein the detectable substances are metal-organic soaps.

8. The method according to any of the preceding claims, wherein the detectable substances are chosen as a sequence of different elements, with distinct spectral lines distinctively, in different and known concentrations, in a host material. twenty-one

9. The method, according to claim 8, wherein the host material is a coating composition.

10. The method according to any of the preceding claims, in which a first sequence of elements is selected and one of a second sequence of elements is mixed with the previous one. 22