DE2020136A1 - Activated bivalent metal halophosphates - prepared by copreciptation - Google Patents

Abstract

A luminescent alkaline earth fluorochlorospatite is precipitated by simultaneously adding first and second reactant soln. in approx. stoichiometric proportions to a stirred precipitation medium. The first solution contains alkaline earth ions, chloride ions and activator ions of antimony or manganese and the second contains phosphate and fluoride ions. The precipitation medium contains water. The phosphor is converted into the final apatite phosphor in a such shorter firing time than the conventional mixture, typically in about 15 mins. Used in coating of fluorescent electric lamps.

Description

Activated Divalent Metal Halophosphates The invention relates to an area of inorganic chemistry, and more particularly relates to processes for the production of activated halophosphates of divalent metals by precipitation. The invention also relates to the intermediate products obtained in these processes and on apatite-like halophosphate luminescent masses from these intermediates can be obtained.

Activated halophosphates of divalent metals are known broadly as the material of the luminescent layer in the usual electrical Fluorescent lamps -related, as they are often used for living room lighting as well for technical and industrial lighting purposes. The texture and the composition of such lIalo genpho sphat luminescent materials are in - patent publications and adequately described in specialist journals. As an example of such Publication is the disclosure of November 22, 1949 to A. H. McKeag and U.S. Patent 2,488,733 issued to P. W. Ranby. As already there is established, the halophosphate luminescent materials are the most naturally occurring Mineral apatite more or less analogous.

Numerous examples of apatite-like halogen phosphate luminescent materials are known in the prior art. These essentially consist of one Base mass, which contains various additives and activator ions, mostly only in smaller proportions. One of the most commonly used ground masses is a calcium fluorophosphate of the formula 3Ca3 (PO4) 2.CaF2. @this composition corresponds that of natural flucrapatite. Build the crystal lattice of the A.patit base mass if ions of the trivalent antimony are added in small proportions, one obtains one Luminous mass, which when excited by ultravoilet radiation with a wavelength of 2537 A fluoresces with emission of a pale blue light. Through appropriate Modifications of the antimony-activated calcium fluorophosphate luminous material with this Normal composition can be qualitative and quantitative changes in the Bring out the nature of the light emitted by the luminous material. So white For example, manganese is a desirable secondary or complementary activator is. Similarly, the fact is known that the luminous material in its peculiarity can be modified in a track that has been lined up for certain purposes, that the calcium in the basic mass is partly replaced by strontium and / or cadmium and partially replacing the fluoride with chloride. The effects of these changes are discussed, for example, in the aforementioned patent by NcKeag and Ranby, also by Gilooly et al. in US Pat. No. 3,109,819 (November 5 1963) and by M. A. Aia et al. In US Pat. No. 2,965,786 (Dec. December 1960).

Gilooly et al. Also emphasize the importance of strict adherence the composition and the difficulties, ie this exact adherence to the Oppose the production of the luminous material according to the known method.

Although luminous materials of this type have been used on a large scale for almost twenty years the manufacturing process is essentially still that revealed by McKeag and Ranby.

From experts in the technology of luminous materials has been for some Zeit supposes that the fine structure of Halophos: has luminous masses that after the known Trocltenbrennverfai) ren are produced, for example so following the method of McKeag and Ranby, is not uniform. Further evidence who apparently confirm this view were taught by Ä.- Wachtel (Journal of the Electrochemical Society, February 1966, pp. 128-134) who has shown that between the outer layer and the core of particles of a calcium halophosphate luminous material, in their structure in the course of a heat compensation process lasting up to 72 hours Manganese and antimony ions had been incorporated, a considerable concentration gradient consisted of manganese and above all of antimony. This inconsistent composition is seen as a serious defect that affects the liet flooring manufactured according to the well-known Luminous mass adheres because si.ch the presence of core parts, which for example the necessary activator proportions are missing, resulting in a reduction in the light yield that would otherwise be achievable. Wachtel's investigation also supports this view.

Attempts have also been made on various occasions to use halophosphate luminous liquids Produce wet process, but here the real @angle of the known Procedure which is based on the necessity of a process of regulated diffusion to run at high temperature in the solid state, not eliminated. Problem solutions of this type are for example in the British patent 614 70Q (December 20, 1948) and in Dutch patent specification 33 992 (December 16, 1948). December 1956), see also British patent specification 717 653 (1954).

Among the objects to be achieved by the invention, First of all, the creation of halophosphate masses of divalent itetals should be mentioned, also the creation of manufacturing processes for Lassen of this kind as well as the creation of halogen phosphate luminescent liquids with an essentially homogeneous microstructure. Further objects and features of the invention result partly from the context of the following statements by themselves and will be otherwise in the following described in more detail.

In one of its aspects, the invention relates to methods of manufacture an apatite-like fluorescent mass by common precipitation, with at least two aqueous solutions of the reactants are mixed together, the summative Phosphate- Fluoride and activator ions and ions of divalent metals which are known to be the basic substance of a halogen phosphate luminous material able to form, and the solutions of the reactants of undissolved fractions are essentially free.

The invention does not extend only to what is outlined above Process, but also to the product manufactured by this process, the as unfired or not heat-treated, formed by common precipitation apatite-like fluorescent mass of an essentially homogeneous microstructure would be to designate, this mass essentially consisting of a bivalent Metal-containing basic substance consists in the activator ions in more uniform Distribution-included.

The through a short burning or through a heat compensation process apatite-like luminous masses according to the invention to be produced from the abovementioned masses with a substantially homogeneous microstructure are also subject to one Aspect of the invention.

A problem that may arise with the procedure just mentioned occurs is that it can sometimes be difficult to prevent premature precipitation of the antimony in the tank to prevent the feed solution in case the solution is not kept at a very high level of acidity. It is known that Antimony salts hydrolyze quite easily and thereby turn into slightly soluble basic compounds pass over. Since it is desirable to make the precipitation of the halophosphate slowly, the antimony feed solution will normally probably last for a period of a few Must remain in the feed solution tank for hours. With moderate degrees of acidity there is then with some likelihood an incipient hydrolytic process Precipitation of the antimony in the feed solution tank before the precipitation of the ealophosphate is finished.

Accordingly, the invention continues to provide more usefulness Procedures for preparing masses of activated divalent halophosphates Metals to the task, but especially the creation of useful methods for Production of such masses by precipitation, and above all avoidance a premature Precipitation of the antimony is envisaged.

A feature that could be described as a second feature of the invention, therefore lies in a method for producing an apatite-like fluorescent mass from a variety of solutions containing summative phosphate, fluoride and activator ions and divalent metal ions for the matrix as essential components the desired apatite-like Fluore scence mass included, this process the implementation of a first solution, which contains as solute substances in which it the salts of the bivalent metals of the basic mass as such or a Mixture of the salts of the divalent metals of the matrix and of the salts the activator metals is, with a second ion solution, the ions of which they are phosphate or fluoride ions, resulting in the formation of an intermediate precipitate leads, wherein in the overall composition of the first and the second solution at least one of the essential components mentioned is missing, whereupon the intermediate precipitate is implemented with a third solution that fixes the missing component or the contains missing ingredients, which are fluoride, phosphate or Activator ions can act, which then finally creates an apatite-like fluorescent mass is formed. The invention extends to those that are not heat-treated as well as the heat-treated apatite-like fluorescent masses that are produced according to the above-described Procedure are produced.

It is therefore obvious that this second feature of the invention an alternative method for introducing the activator ions into the by precipitation contains obtained halophosphate compositions, through which a rapid addition of the Activator ions containing solution is made possible, without prejudice to the fact that the main precipitation process extends over a longer period of time. This is special advantageous when antimony ions or other ions are to be incorporated, which may be difficult to keep in solution if the solution is prolonged Time left in the container for the Beschi ¢ kungslögung. This also provides a guarantee for considerable flexibility in the use of precipitation processes for manufacture apatite-like luminous mass. So can in this case for example a number of luminescent materials that differ only in the activator content a single set of stock solutions can be prepared for the matrix, wherein the respective activators to the slurries of the intermediate precipitation product can be added.

A third feature of the invention is based on the knowledge that a practical advantage is associated with carrying out the precipitation at elevated temperatures. In most cases this is normal room temperature or one of this only slightly different temperature obtained precipitation product from extremely small Xrystallites. This product has a gel-like structure and is very heavy to filter and wash out. The product also normally delivers when dry extremely hard Elümpohen. If, on the other hand, the precipitation is taken at higher temperatures before (60-900C), one normally obtains relatively uniform, granular precipitation products, which are much easier to filter and wash out than those at room temperature precipitated products. Filling products of this type usually yield when dried a soft, crumbly mass cake. However, these contain precipitation products mostly a substance which, when burning, leads to the formation of ß-tricalcium phosphate secondary phase leads.

The invention therefore also has the object of providing a method for the production of calcium-maltous masses of halogen phosphates of the alkaline earth metals to be created by a precipitation carried out according to appropriate methods, whereby it is ensured that there is essentially no B-tricalcium phosphate in the fired product is included.

With regard to the third feature of the invention, it should now be noted that it is in the representation of calcium-containing halophosphates of the alkaline earth metals according to the wet process disclosed here elsewhere, a critical temperature gives. It has been shown that when the precipitation is carried out in a The only temperature in the fired luminous material that does not exceed 560C secondary phase of some importance a pyrophosphate phase appears. If you take over the precipitation at temperatures 560C before so receives the secondary phase of some importance is a tricalcium phosphate phase. As will be explained below, this fact applies particularly to the Production of such luminous masses in the form of calcium-containing halogen phosphates of the alkaline earth metals where the use of manganese as an activator is intended.

It is known that the lignan content in one of a calcium-containing Halogen phosphate of an alkaline earth metal existing luminous material of considerable importance for the color quality of the light emitted by this luminous material. In the Manufacture of luminous materials that emit light of a certain color quality it is important to keep the manganese content within very narrow limits and carefully avoid everything that the normal relationships between the color quality and could interfere with the manganese content.

Although it is desirable to include one of a halophosphate Alkaline earth metal existing luminous material both the content of the calcium pyrophosphate phase as well as that of the tricalcium phosphate phase has to be kept as low as possible but it has been shown that the presence of the latter is particularly evident harmful effects. This is due to the fact that there, '' the presence a tricalcium phosphate phase the normal relationships between the Iangan content and interferes with the color quality of the emitted light. This is expressed in a lower red component of the emitted light than it is due to the manganese content the luminous material would normally be expected.

It has been suggested that a tricalcium phosphate phase selectively adsorbed manganese, so that only a lower proportion of manganese in the ratio remains, which then acts as an activator in the halophosphate lattice. These The view coincides with the observation facts.

Regardless of the correctness of the theoretical i outlined above However, with regard to the third invention, consideration can be given to the determination be taken that when the calcium-containing halophosphate is precipitated Alkaline earth metal a temperature not exceeding 560C, the luminescent material obtained in this way is essentially free of a tricalcium phosphate phase after firing is, and that the color quality of the light emitted in this case of those corresponds to what one would expect based on knowledge of the manganese content of the total mass should.

Although the test results listed below show that that both at room temperature and at any elevated temperature up to 560C i'Ellung products can be obtained, which are essentially free of ß-tricalcium phosphate are as the secondary phase, the precipitation is, however, preferably at temperatures made, which are close to 5600, but do not exceed this Tempern turwert.

In contrast to the processes known from the prior art come within the framework of the method according to the invention according to one aspect of the same Solutions of the reaction partners in use in which all types of ions are dissolved are, which should also be contained in the crystal lattice of the finished luminous material. This is made possible by the fact that one chemically incompatible ion species, i. E those types of ions which form water-insoluble compounds with one another react until the point in time in which it keeps in stock in separate solutions by mixing these together to form a precipitated product by common precipitation to produce, which has the apatite structure and all the necessary types of ions essentially in the desired proportions in the crystal structure contains. The presence of the apati.t structure is not only due to X-ray diffraction studies can be recognized, but also by the fact that the dried, but not yet fired, precipitate when exposed to ultraviolet radiation Fluorescent with the typical emission spectrum of the calcium halophosphate system.

The firing or heat treatment then brings about the fluorescent properties fully usable, as this increases the size of the crystallites and lattice disorder be "smoothed out".

This is already the case with a relatively short duration of the heat compensation process achieved, in contrast to the lengthy burning, as is the case with the known processes is required to To induce reactions in the solid state and to cause the ions to diffuse into the crystal lattice. It lies it is obvious that the duration of the heat treatment process depends on the amount of Thermally processed material is subject to fluctuations, but this time span is in any case relatively short compared to the previously required burning time. The heat remuneration or thermal work-up can take place in a nitrogen atmosphere or in an atmosphere of another inert gas as well as in air be made.

Because of the different chemical nature of the existing Ion species will normally be at least one of the solutions of the reactants be a bit acidic, a second, on the other hand, a bit alkaline. This may be necessary to prevent hydrolytic precipitation or to ensure complete dissolution of the substances to be dissolved and the stability of the solutions.

The acidity / alkalinity of the precipitation mixture is preferred kept in the range of PH 6-8. But there is often also a larger deviation acceptable in the range of approximately PH 5-9. Higher levels of acidity or alkalinity can still be portable in certain cases but are usually avoided.

The pEI setting can be set via the acidity / alkalinity of a or more than one of the reagent solutions can be made or one can in the course of the process operations at the same time continuously measure an acidic and / or basic solution.

Of course, the solutions of the reactants should not contain any ions, which have a harmful effect on the apatite-like luminous masses. For the purposes in question within the scope of the invention, such types of ions must are considered harmful, if they are present in an apatite-like luminous material, disadvantageous Effects on the performance of this luminous material are to be feared, and, moreover, in the normal processing process not to a harmless one Proportional content in the thermally processed luminous mass can be brought, for example by washing out or leaching in the wet phase of the processing step or by volatilization in the thermal phase Work-up.

If the presence of chloride is desired in the luminous material, so this can be in the form of hydrochloric acid or in the form of suitable chloride salts introduced into one of the solutions of the reactants or into the precipitation medium will.

Favorable effects can be passed through to a certain extent achieve digestion of the precipitate. Digesting can be done in such a way that the precipitate is resuspended in distilled water and the slurry heated for a few hours. 'gives a determination that in the crystal structure in addition If a chloride content is still required, the chloride content can if desired be increased by adding chloride ions to the digestion agent. gives.

The amount of chloride ions present in the end product becomes influenced by various factors. This includes the peculiarity of the solutions the reaction partner and the precipitation mixture, i.e. the pH-lert, the concentration, the stoichiometric composition and the absence or presence and the concentration of additionally introduced chloride components. The proportion the existing chloride is also influenced by the working conditions during digestion, namely on the duration, the temperature control, the chloride concentration and the composition of the precipitation product. Suitable conditions to achieve a certain result must be adhered to must be determined empirically.

The chloride content of the fired luminous material is still subject also an influence by the procedure followed in the Wc ', rmevergutung and through the working conditions that are complied with.

Compared to the known procedures for the production of Halogen phosphate luminescent materials are offered by the method according to the invention within the framework of this what is known as the total solution method is followed, several Advantages. For example, within the scope of the invention, this can be used as an intermediate product accruing halophosphate with a much shorter period of time thermal Reconditioning can be converted into an apatite-like luminous substance than the known physical mixture of solid phases.

This procedure also eliminates the need for mass transport fairly heavy or volatile types of atoms by diffusion in the solid state. About that In addition, there is the possibility of a simpler and more precise setting the homogeneity and the composition than in the known procedures.

The second feature of the invention can be in many different ways Find embodiment. If it is the desired luminous material, for example should be an antimony-activated calcium fluorochlorophosphate, so can in a a calcium chloride solution is reacted with a solution in the first step, the phosphate and fluoride ions in approximately the stoichiometric proportions contains how they are aimed for the finished luminous material. Here are the usual precautionary measures to be observed; to keep ions away, their presence in the finished luminous material would be undesirable and their concentration in the normal Processing rate would not be reduced to such an extent that their content is in the fired luminous material is harmless, for example by washing out or Leaching in the wet operations of the process or by volatilization the thermal processing. One solution of the reactants is preferred a bit acidic and the other a bit basic. Usually then the two of them Solutions of the reactants are added to a third reaction vessel, the water Contains as a reaction medium. The solutions are preferably added below vigorous stirring in stoichiometrically equivalent throughput ratios O Normally the reaction mixture will be kept approximately neutral, that is to say in a pH range from about 6 to 8. However, depending on the particular circumstances, often larger ones can also be used Fluctuations are accepted.

In the case considered here, after the precipitation of the calcium halophosphate base mass the antimony activator is added to the precipitation slurry, expediently in the form of an antimony trichloride solution. The activator substance is here quickly built into the calcium halophosphate matrix and the product thus obtained can then immediately be filtered off, washed and dried will. The dried product has the apatite crystal structure as shown by X-ray diffraction can be recognized, and it fluoresces with short-wave ultraviolet radiation (2537 A).

Through a relatively short thermal work-up at 10500 C the fluorescence display shafts are fully brought to bear, that the material in this respect corresponds to the commercially available luminous masses of this general Type is comparable.

As part of a modified procedure, the antimony activator be introduced into the same solution that also contains the calcium ions, and the fluoride content of the phosphate solution can be omitted. The fluoride can then be added is added to the formation of an intermediate precipitate calcium carbon phosphate / Sb in order to obtain the desired antimony activated calcium fluorine chlorpho sphat form.

A modification is also possible in such a way that initially by reacting a calcium and a phosphate salt solution an Oalciumpho sphat-Zwi is formed, - whereupon the slurry of this intermediate precipitate roduct s is mixed with solutions that contain antimony (III) and fluoride ions, in order to form the desired apatite-like luminous material.

Another possible modification is that you first Solutions of calcium and fluoride ions react with one another to form an intermediate to obtain a calcium fluoride slurry to which solutions are then added, which contain antimony and phosphate ions, leading to the formation of the antimony activated Calcium halophosphate leads as an end product.

Other modifications are also possible. If it is, for example should be desired, some of the calcium content in the antimony activated potassium halophosphate to be replaced by strontium and / or cadmium, these substance components can either already introduced into the stock solution containing the caloium ions and consequently in the first step, or they can be canceled at a later point in time. bring in by appropriate treatment of the intermediate precipitation product.

If the presence of manganese as a complementary activator substance is desired, this can be done simultaneously with the antimony in a corresponding manner be introduced, or one of these substances can be added to the intermediate precipitation product add and the other by a treatment subsequent to the precipitation process bring in.

It should be clear that normally the presence of chloride is desirable in the halophosphate matrix. Should be the presence of chloride however, once not desired, other water-soluble compounds may be used divalent metals are used, for example nitrates, Acetates, bromides and iodides can act. Similarly, instead of the above divalent metals or, in addition to these, if desired, others, such as for example barium, zinc, magnesium or the like can be introduced.

The following exemplary embodiments illustrate the first aspect of the invention or the first feature of the invention, the so-called total solution method.

Working Examples 1-4 Procedure I Composition: Solution A (cation solution) By dissolving calcium chloride, antimony trioxide and strontium or cadmium carbonate in dilute hydrochloric acid became a clear solution of calcium chloride, Antimony trichloride and strontium or cadmium chloride produced, whereupon mixed with manganese nitrate solution and with water to a predetermined volume was filled.

Solution B (anion solution) Mnm'oniun'hyirogenpho sphat and ammonium fluoride were dissolved in dilute ammonia solution and this solution was made up with water filled up to a predetermined volume.

The details are given in Table 1.

Precipitation: Solutions A and B were simultaneously under vigorous Stir and in compliance with equivalent throughput ratios in a precipitation vessel measured that contained a measured volume of water. As a result, the The pH of the filling slurry is within a relatively narrow range be kept constant. After the addition was complete, the slurry became still Stirred for a while and then filtered, whereupon the filter cake thoroughly was washed out.

Digesting and drying: the washed-out precipitation product (the filter cake) was resuspended in water. In some cases the filter cake was in divided into two or three aliquots and the aqueous medium was made with hydrochloric acid or mixed with ammonium chloride. Most of the time the slurry was at one temperature heated from 70 to 950 and allowed to stand for a few hours before filtration. Of the filter cake obtained in this way was washed out with water, dried at 12500 and grind. The details are given in Table 2.

Table 1 Components of solution A (cation solution) and the solution B (anion solution) of the working examples 1-4, example no.

Substance components 1 2 3 4 Solution A: CaCl2 # 2H2O (grams) 912.9 912.9 929.9 456.5 Sb2O3 "8.20 8.20 8.20 4.51 SrCO3" 24.91 24.91 - 6.23 CdCO3 "- - 8.64 7.27 Mn (NO3) 2 "33.55 33.55 33.55 18.45 HCl (mole) 1.2 1.2 0.98 0.65 total volume (Liters) 4 4 4 2 Solution B: (NH4) 2HPO4 (grams) 563.1 563.1 613.0 286.5 NH4F "36.71 44.75 36.70 20.13 NH4OH (moles) 4.80 4.70 3.95 2.34 Total volume (liters) 4 4 4 4 Tabel 2 Precipitation and digestion conditions in the working examples 1-4 process conditions Embodiment No.

during the precipitation i 2 3 4 solution A: initial temperature t ° C) room temp. 29 28 Rasumtemp 0.13 0.06 0.22 0.32 Solution B: initial temperature (° C) room temp. 31 28 room temp.

PH 9.9 9.60 9.47 9.40 Precipitation slurry: initial volume of water 2 2 2 1 (liter) Duration of the precipitation 24 23 27 28 process (min) PH range at of the precipitation 7.0-7.52 7.0-7.6 6.1-6.8 7.0-8.8 at the end of the precipitation 7.52. 7.18 6.5 7.45 Duration of stirring after precipitation (min) 30 30 15 15 Tabel 2 (continued) Precipitation and digestion conditions in the exemplary embodiments 1-4 process conditions embodiment no.

During digestion 1 2 3 4 Part X: total volume of the up @ 3 35 13 Sole insulation (liters) Dissolved additions none none none none Initial temperature (° C) room temp. 35 28 approx.

max.temperature (° C) 90 90 70 approx. 26 duration of heating 50 40-50 no mung (min) heating.

Time from completion of heating 16 21 17 17 to filtration (Hours) Part Y: total volume of the slurry 2 3 + 1.3 (liter) addition of dissolved matter 0.12 0.12 none (mol HCl) start temperature (° C) room temp. 29.5 approx. 26 maximum temperature (° C) 90 93 70 Duration of heating (min) 35 25 Duration of the completion of the Warming approx. 16 approx. 22 approx. 17 until filtering (hours) + the filter cake was divided into two subsets, each of which was digested in the same way as Part X. Both parts were used for filtration and further treatment united with each other.

Table 2 (continued) Precipitation and digestion conditions for the Working examples 1-4 process conditions working example no.

when digesting 1 2 3 4 Part Z: total volume of the 2 3 not digested slurry (liter) addition of dissolved 100 100 (grams of NH4Cl) initial temperature (° C) room temp. 31 max.temperature (° C) 90 90 Duration of heating (min) Duration from the completion of the heating 16 23 to the filtration (hrs.) procedure II Embodiment 5 antimony trioxide (2.25 g Sb203) and strontium carbonate (6.23 g SrCO3) were dissolved in a solution, the hydrochloric acid (24.5 ml of an approximately 37 per cent. HCl) and calcium chloride (172.3 g CaCl2).

Manganese nitrate solution [9.23 g Mn (NO3) 2] was added and that The mixed solution was made up to 1000 ml (solution A).

Diammonium hydrogen phosphate [143.2 g (NH4) 2HPC4] and ammonium fluoride (11.17 g NH4F) was dissolved in water and the solution was made up to 2000 ml (Solution B).

An ammonia solution (73 ml of a solution with approximately 30% NH @) was made up to 1000 ml (solution C).

3 Solutions A and B were at equivalent throughput ratio to the solution over a period of 75 minutes with stirring at room temperature C added. The precipitation slurry was at pH at the end of the addition of 5.3.

The slurry was filtered and the filter cake was washed out and dried at 12500.

Exemplary embodiment 6 The dried products of the exemplary embodiments 1 to 5 were ground to a particle size smaller than the US standard sieve with 140 meshes per inch (corresponding to a particle size of less al 0.10 mm) and small portions were each in a period of about 15 minutes Thermally worked up at a temperature of 1050 to 1150 ° C.

The chemical analyzes of some of the not thermally processed Products of embodiments 1 to 5 and some of the thermally processed Products of embodiment 6 are listed in Table 3. The thermal Reconditioned products are indicated by the letters TA after the numbers of the relevant Embodiments such as those used here to denote the non-calcined intermediates serve, identified.

Table 3 Chemical composition of non-thermally processed and thermally processed apatite-like halophosphates (expressed as Atomic or ionic ratio of the halide and metal ions to 6 mol PO4 each) Weight Execution ----------------------- Gram Atom --------------------- Mol lust for example no. Ca Sr Cd Mn Sb Cl F PO4 burning (%) 1X 8.68 0.24 - 0.25 0.077 0.46 1.35 6.00 8.0 1Y 8.67 0.23 - 0.25 0.081 0.50 1.37 6.00 8.5 1Z 8.68 0.24 - 0.24 0.072 1.97 1.36 6.00 15.5 2X 5.5 2Y 6.0 2Z 9.5 3 8.56 - 0.39 0.25 0.073 0.15 1.32 6.00 4.5 7 - 9.90 1XTA 8.77 0.23 - 0.25 0.069 0.18 1.31 6.00 1YTA 8.69 0.24 - 0.25 0.063 0.15 1.32 6.00 1ZTA 8.68 0.23 - 0.25 0.031 0.24 1.27 6.00 Tabel 3 (continued) Chemical composition of non-thermally reclaimed and of thermally processed apatite-like halogen phosphates (expressed as atomic or ion ratio of the halide and metal ions to 6 moles of PO4 each) ----------------------- Gram atom --------------------- Mol lust in example no . Ca Sr Cd Mn Sb Cl F PO4 Burning (%) 2XTA 8.83 0.25-0.25 0.071 0.033 1.61 6.00 2YTA 8.86 0.23 - 0.25 0.071 0.033 1.61 6.00 2ZTA 8.82 0.25 - 0.25 0.057 0.056 1.59 6.00 3TA 8.75 - 0.054 0.25 0.068 0.10 1.27 6.00 4ZTA 8.45 0.11 0.11 0.29 0.080 0.061 1.34 6.00 The dried, thermally unprocessed products of the embodiments 1 to 5 were with the short-wave ultraviolet radiation (2537 A) irradiated with a mercury vapor lamp.

Each of these products fluoresced clearly upon irradiation.

The crystal structure of the non-thermally processed products was subjected to an X-ray diffraction study. Everyone's diffraction pattern showed lines typical of the apatite crystal structure, with the width the lines indicated that the crystallites were very small.

The luminous power of the halogen phosphate luminous materials of the execution case game 6 with irradiation with the Gellenlange 2537 A was carried out by means of a hand-held Filter photometer compared with that of a commercially available "warm white" luminous material. The response behavior of the filter photometer used to "white" light can be determined approximate that of the human eye through a corresponding setting. The photometer readings are listed in column A of Table 4. Those in columns B and C of the table 4 readings compiled were with a red filter or with a blue filter and leave the relative intensity of the red and blue components recognize the light emitted by the luminous masses. Higher readings are synonymous with higher light output.

The X-ray diffraction patterns of the thermally processed products correspond to that of a well-crystallized calcium fluorapatite (American standard ASfflI pattern 15-876). The small deviations to be expected are shown in the unit cell dimensions obtained by incorporating the various cationic or anionic additives are caused in the crystal lattice. Act sometimes small proportions of secondary phases such as Ca2P207 can also be found.

Table 4 Relative brightness A B C (filer with the (red filter) (blue filter) Luminous material response behavior of the eye) 1XTA 72 51 25 1YTb 74 51 26 1ZTA 55 39 21 2xTA 75 48 24 2YTA 79 49 .24 2ZTA 81 53 26 3 TA 81 55 27 4XTA 67 41 24 4? TA 65 39 25 4ZTA 84 56 23 7 TA 77 50 24 commercially available 78 56 21 warm white The following Exemplary embodiments serve to illustrate the feature described above was designated as the second feature of the invention.

Working examples 7-10 Composition of solution A (cation solution) By dissolving acid-soluble compounds of the intended metals in dilute Hydrochloric acid was made a clear acidic solution and this was mixed with water filled up to a total volume of 1 liter.

Solution B (anion solution) diammonium hydrogen phosphate and ammonium fluoride were dissolved in dilute ammonia solution and the resulting solution was with Water made up to a total volume of 2 liters.

You used substance components in the preparation of solutions A and B. are listed in Table 5.

Precipitation: Solutions A and B were, simultaneously, under vigorous Stir at an addition rate of 100 ml / min and 200 ml / min, respectively placed in a precipitation vessel containing 500 ml of water. At the end of the precipitation process the pelling slurry was neutral to slightly alkaline (PH 7-8).

Treatment after precipitation: In the working examples 7 and 10, the slurry became for further treatment after the completion of the precipitation process divided into two approximately equal subsets (X and Y). With the exception of those in table 6 cases marked in this sense became the vigorously stirred slurry each with Mn (II) salt and / or Sb (III) salt added as activator substance. That Mn (II) salt was added as an approximately 58 percent solution of Kn (NO3) 2 the Sb (III) salt, on the other hand, is in the form of a solution which is obtained by dissolving Sb203 in a salt acid ammonium chloride solution was prepared.

Unless otherwise determined in individual cases, the mixtures obtained in this way were each after the addition of the activator solutions immediately filtered off. The precipitate was then washed out at 1250C dried and ground to a particle size less than the US standard sieve with 140 meshes per inch (particle size smaller than about Q.10 mm).

The details are given in Table 6.

Table 5 Components of solutions A and B (working examples 7-10) Embodiment No.

Substance components 7 8 9 10 solution d: C @ Cl2 (grams) 274.6 274.6 274.6 274.6 SrCO3 "- 3.69 3.69 3.69 CdCO3" - 4.31 4.31 4.31 Mn (NO3) 2 "- - 7.58 -Sb2O3 "- - - 5.46 hydrochloric acid (ml of a 30 36 41 41 37% HCl) solution B: (NH4) 2HPO4 (grams) 198.1 198.1 198.1 198.1 NH4F "17.4 15.7 15.7 15.7 NH4OH (mole) 1.75 1.97 1.86 1.86 Table 6 Additions after the precipitation Embodiment No.

Additive 7 8 9 10 X Y X Y Mn (NO3) 2 (grams) - 4.37 7.58 - 3.79 -Sb (III) solution - 25 100 65 - - (volume in ml) i Sb2O3 (grams) 1.82 5.46 5.46 5.46 hydrochloric acid 5 15 15 (ml of 37% HCl) NH4Cl (grams) 10 sat. ++ X Y + + + + slurry before stirring for 15 minutes before filtering ++ 50 ml of a saturated NH4Cl solution Embodiment 11 Solution A A clear acidic solution of the kind required for an apatite-like luminous material Cations were made by dissolving the following compounds in a hydrochloric acid solution (Content 41 ml of 37 percent HCl) and then filling up the clear prepared in this way Solution prepared with water to a total volume of 1 liter.

CaCl2 260.9 g SrCO3 3.68 g CdCO3 4.31 g Mn (g03) 2 7.58 g (in the form of a 58% solution) Sb203 5.19 g of solution 3 diammonium hydrogen phosphate (198.1 g) was dissolved in dilute ammonia solution (1.77 mol NH4OH) and the resulting Solution was made up to a total volume of 2 liters with water.

Preliminary Precipitation: Solutions A and B were taking simultaneously vigorous stirring at an addition rate of approximately 100 ml / min respectively of 200 ml / min in a precipitation vessel which contained about 500 ml of water. At the At the end of the precipitation process the slurry was neutral to slightly alkaline (PH 7-8).

Further treatment One liter of an ammonium fluoride solution (7.44 g NH4F) was added to one half of the range at a rate of addition of about 100 ml / min Given slurry, the preparation of which is described in the previous paragraph is. The thus treated reslurry was filtered and the precipitate became washed, dried and ground in the same way as the previous ones Embodiments 7 to 10 is described.

Embodiment 12 Solution A A clear acidic solution was passed through Dissolution of the calcium chloride and strontium carbonate idengen mentioned in exemplary embodiment 11 and cadmium carbonate in a hydrochloric acid solution (content 26 ml of 37 percent HCl) and by making up the clear solution thus prepared with water to a total volume made from 1 liter.

Solution B A solution of ammonium phosphate was made in the same way as prepared in embodiment 11.

Preliminary precipitation: This process step was also carried out in in the same way as described in embodiment 11.

Further treatment: Na, ch-completion of the preliminary precipitation has been carried out the slurry with solutions of manganese nitrát [5B percent solution with a content of 7.58 g of Mn (NO3) 2] and of hntimony trichloride / ammonium chloride (5.19 g of Sb203 and 15 g of NH4Cl dissolved in 50 ml of a hydrochloric acid solution containing 15 ml of a 37 percent HCl) added.

One liter of an ammonium fluoride solution was then added to the slurry thus treated (14.88 g NH4E) was added at a rate of about 100 ml / min. The slurry was then finally filtered and the precipitate became washed, dried and ground in the same way as in the previous ones Embodiments 7 to 10 is described.

Embodiment 13 A solution of ammonium fluoride (14.88 g NH4F in 500 ml of water) slowly became a vigorously stirred acidic solution of chlorides Add divalent metals obtained by dissolving 260.9 g of Ca012, 3.69 g SrCO3 and 4.31 g of CdCO3 in a solution made up to 800 ml of -41 ml of a 37% Hydrochloric acid was prepared. Lean gan nitrate became in this strongly acidic slurry [7.58 g Mn (N03) 2 in the form of a 58 percent solution] and antimony trioxide (5.19 g) solved. After the activator substances had been added, the mixture was added at one rate of about 100 ml / min with an ammonium phosphate solution 0198.1 g (NH4) 2HPO4, 1.77 mol NH OH in a total volume of 2000 ml-] added. The product thus obtained became filtered, washed, dried and ground as in the previous ones Embodiments 7 to 10 is described.

.Example 14 proportions of the dried and powdered Products of working examples 7 to 13 were placed in quartz vessels while heated to 1050 ° C for a period of 90 minutes and then additionally for kept at this temperature for a certain period of time (in the case of the products of the Working examples 7 to 10 each 15 minutes, in the pallet of the products of the working examples 11 to 13 against 30 minutes). For products 7X and 7Y, the heat treatment made in the covered pan; the remaining products were used for heat treatment put in a boat which was inserted into a quartz tube, whereupon a slow one Nitrogen stream was passed over. The thermally reconditioned products were somewhat sintered together, but could easily be ground to a powder.

The chemical analyzes of some of the not thermally processed Products d'er Embodiments 7 to 13 and some of the thermally processed ones Products of embodiment 14 are given in Table 7. The thermally processed Products are indicated by the letters TA after the on the relevant embodiment related designations for the intermediate products that have not been thermally processed identified.

Table 7 Chemical composition of non-thermally processed and thermally processed apatite-like halophosphates (expressed as Atomic or ionic ratio of the halide and metal ions to 6 mol PO4 each) Execution -------------------------- Gram atom --------------------- --- Mol example No. Ca Sr Cd Mn Sb Cl F PO4 8X 9.09 0.10 0.07 0.16 0.13 2.21 1.67 6.00 8XTA 9.26 0.10 0.07 0.16 0.07 0.07 1.63 6.00 11 8.81 0.095 0.090 0.14 0.13 0.48 1.52 6.00 11TA 8.92 0.094 0.087 0.14 0.07 0.06 1.57 6.00 The dried ones thermally unprocessed products of the working examples 7 to 13 were with the short-wave ultraviolet radiation (2537 A) from a mercury vapor lamp irradiated. With the exception of the (non-activated) product 7X, each of these fluoresced Products clearly when irradiated.

The crystal structure of the non-thermally processed products was subjected to an X-ray diffraction study. Everyone's diffraction pattern showed lines typical of the apatite crystal structure, with the width the lines indicated that the crystallites were very small.

The X-ray diffraction patterns of the thermally processed products correspond to those of a well-crystallized calcium fluorapatite (American Norm ASBI pattern 15-876) * The expected small deviations are shown in the unit cell dimensions obtained by incorporating the various cationic or anionic additives are caused in the crystal lattice. EEnnter have an effect also small proportions of secondary phases such as Ca2P207.

The luminous efficacy of the halogen phosphate luminous materials of the exemplary embodiment 14 with ultraviolet irradiation with 2537 A was measured by means of a commercially available filter photometer compared to that of a commercial sublime "cold white" luminous material. The results are summarized in Table 8 (see in this context also those of the table 4 preliminary remarks about the statement.

readability).

Table 8 A B C (filter with the (red filter) (blue filter) luminous material Response behavior of the eye) Commercially 80 48 42 x old white 80 48 4? 7YTA 59 32 31 8XTA 7j 43 42 8YTA 77 44 41 9 TA 79 46 41 10XTA 80 46 44 10YTA 52 14 88 11 TA 82 48 42 12 TA 80 48 43 13 TA 80 44 46 The following exemplary embodiments serve to illustrate the feature mentioned above as a third invention feature was designated.

Embodiment 1-5 A series of eight calcium-containing luminous masses, at them. it was halophosphates of alkaline earth metals, was after the so-called total solution method described in the above in Examples 1 to 5 produced by precipitation from aqueous solution. The only major difference in the process conditions was the precipitation temperature.

This fluctuated in the series between 24 and 830C, but became the Temperature of the slurry for each of the preparations throughout the precipitation process kept constant.

A cation solution (1000 ml) was prepared for each of the preparations, which contained the following components: CaCl2 188.5 g hydrochloric acid (37% HCl) 24.5 ml SrCO3 2.67 g CdCO3 3.12 g MnC12 6.99 g Sb203 3.96 g The carbonates Des.Strontium and cadmium as well as the antimony trioxide were in'der acidified solution completely soluble, so that a clear solution was formed.

A series of anion solutions was prepared in a similar manner, those in a total volume of 1500 ml each 143.2 g (NE4) 2HP04 and 11.17 g NH4F contained. The anion solutions also contained ammonium hydroxide, namely each in different proportions depending on the precipitation temperature in order to To achieve this way that the final pH values were reasonably uniform.

The cation and anion solutions were each time during one Period of time from 60 to 75 minutes with stirring at the stoichiometrically equivalent addition rate given in 600 ml of water. The temperature of the precipitation slurry thereby became for the duration of the precipitation process, always with a maximum deviation of + 100 kept constant. The deviations in the respective procedural conditions observed are given in Table 9.

Table 9 -------------- Approach-procedural variable A B C D E F G H Precipitation temperature (° C) 24 28- 42 51 56 59 73 83 Reagent volume NH OH (27% NH -) in the 4 78 80 84 88 89 89 98 110 anion solution (ml) final pH value of the Slurry 7.3 7.5 7.8 7.4 7.9-6.9 7.5 7.6 The washed products were dried at 125 ° C and then fired at 1050 ° C, one portion each in a covered Crucible in the air and a second part in a nitrogen atmosphere.

Completely chemical analyzes were carried out according to the usual methods carried out for investigation on the wet road. The converted to molar ratios Test results are for the portions burned in a nitrogen atmosphere listed in Table 10. Similar results were obtained with those fired in the open air Get Shares. (The theoretical manganese content is 0.3 gram atom Mn on each 6 table 10 analyzes - of halophosphate luminous masses, which in a A nitrogen atmosphere were burned (expressed as an atomic or ionic ratio of halide and metal ions on 6 moles of PO4 each) -------- gram atom on 6 each Mol PO4 luminous substance Ca Cd Sr Mn Sb F Cl A 8.76 0.07 0.09 0.30 0.05 1.58 0.01 3 8.75 0.07 0.09 0.30 o. O6 1.63 0.02 C 8.85 0.07 0.09 0.29 0.06 1.60 0.06 D 8.81 0.07 0.09 0.29 0.04 1.55 0.06 E 9.03 0.07 0.08 0.30 0.07 1.65 0.10 F + 9.57 0.08 0.09 0.32 0.09 1.75 0.02 G 9w34 0.07 0.09 0.31 0.05 1.64 0. Q5 H 9.29 0.07 0.09 0.30 0.07 1.57 0 0.03 + The numerical values suggest that the phosphate value given for this sample was too low. The X-ray diffraction patterns indicate the presence of a small proportion Ca2P207 as a secondary phase in the luminous substances A to E as well as the presence of a detect a small proportion of ß-tricalcium phosphate in the luminous masses F to H.

to compare the intensity and color quality of the broadcast Light was the light yield of Examined panels that irradiated with short-wave ultraviolet radiation (2537 A) became. The photometer readings are for "white" light. in table 11 reported as "luminance" values. For those also listed in Table 11 Red and blue values are correction values that are used for better comparison the color quality of the light emitted by the various luminous materials Standard luminance value of 80 was used. The ones contained in Table 11 Numerical values were obtained when examining those fired in a nitrogen atmosphere Luminous masses determined. Similar results were obtained for those fired in the open air Luminous masses preserved.

Table 11 Comparative photometer readings from luminous panels when irradiated with 2557 A emitted light (red and blue values on a Standard luminance of 80 corrected) red blue luminance luminance (corrected) (corrected) A 89.5 51.5 17.5 B 87 51.5 18 c 86 54 19.5 D 85 54 19.5 E 81 55 20.5 F 74 48.5 37 G 72 47 37.5 H 67 45 44.5 It can therefore be seen that the comparative values in Table 11 for the luminous masses A to E turn out to be fairly uniform. These Luminous masses had precipitated out at temperatures not exceeding 560C. At the same time it is noticeable that the red component in the light of the luminous masses F to H (which had been precipitated at temperatures above 560C) is considerably weaker than with luminous masses A to E.

Working example 16 There were two further series of luminous masses produced similar to those of the embodiment 15 and also in a similarly quiet manner rated as described in working example 15 isS; whereby In this case, however, the manganese content is 0.19 gram atom of Mn, respectively was 0.55 gram atom of Mn for every 6 moles of PO4. Generally comparable Results obtained, albeit those occurring at precipitation temperatures higher than 5600 The shift in color quality in the series with the high manganese content is less pronounced than with lower manganese levels.

In summary, it can be said that all of the Objects solved by the invention and furthermore achieved further advantages will.

Changes may be made to the products and procedures described above are made, which also fall within the scope of the invention, and the The details described are for purposes of illustration only therefore not to be construed in a limiting sense of the invention.

Claims (16)

(New) claims 1. Apatite-like fluorescent mass, characterized by an essentially homogeneous microstructure, with a basic mass of at least one halogen phosphate, preferably from a fluorochlorophosphate of a divalent metal, preferably an alkaline earth metal and / or cadmium, activator ions evenly distributed are. 2. fluorescent composition according to claim 1, characterized in that in the basic mass of at least one fluorochlorophosphate of calcium, strontium and / or cadmium an antimony (III) or nanganese compound as an activator uniformly is distributed. 3. fluorescent composition according to claim 1, characterized by the components Alkaline earth manganese fluorochlorophosphate, preferably strontium or calcium manganese fluorochlorophosphate, as a matrix and antimony (III) compound as an activator. 4. Process for the production of an apatite-like fluorescent mass according to one of claims 1 to 3 by co-precipitation, characterized in that at least two aqueous solutions free of undissolved material are mixed with one another, the phosphate, fluoride and activator ions, preferably antimony (III) - or nanoscale anions, as well as bivalent ones, to form the basic material of a halogen phosphate luminous material suitable Metal ions preferably contain calcium ions, whereupon the resulting wet, if necessary, thermally for a relatively short period of time is treated. 5. The method according to claim 4, characterized in that the pH of the reaction mixture between about 6 and about 8 is adjusted. 6. The method according to claim 4 or 5, characterized} that one Solution containing activator ions and divalent metal ions and a phosphate and solution containing fluoride ions are added together by simultaneously be added or added to a reaction vessel at equivalent rates. the solution containing the activator ions and divalent metal ions into an equivalent Given proportions of reaction vessel containing phosphate and fluoride ions will. 7. The method according to claim 6, characterized in that the A solution containing activator ions and divalent metal ions has an essential role Has proportion of chloride ions. 8. The method according to claim 4 for the preparation of a luminescent Alkaline earth fluorochlorapatite, characterized in that one of the alkaline earth and chloride ions, preferably calcium chloride and one phosphate and fluoride ions, preferably Solution containing diammonium hydrogen phosphate and ammonium fluoride at the same time Stirring can be added to an aqueous precipitation medium. 9. Verfaluten according to claim 8, characterized in that in the Solution containing phosphate and fluoride ions or additionally in the precipitation medium ahloridionen are included. 10q method according to claim 8 or 9, characterized in that the Solution containing alkaline earth and chloride ions as antimony ions or manganese ions Contains activator ions. 11. The method according to claim 8, 9 or 10, characterized in that that the pH of the precipitation medium after adding the two solutions between about 6 and about 8 is set. 12. The method according to claim 4 for producing an apatite-like Alkaline earth phosphate bluorescence measures, characterized in that it has a solution of salts of the divalent metals and optionally of salts of the activator metals is unset with a solution containing phosphate and / or fluoride ions, wherein in the total composition of the two solutions phosphate, fluoride and activator ions and divalent metal ions, mostly alkaline earth ions, except for at least one of these ion groups are present, whereupon the intermediate precipitate thus obtained with another one containing the missing fluoride, phosphate and / or activator ions Solution is brought together. 13. The method according to claim 12, characterized in that a A solution containing alkaline earth metal chloride with a solution containing phosphate and fluoride ions Solution is reacted, and then a solution containing activator ions is added is or a solution containing an alkaline earth metal chloride and antimony ions a solution containing phosphate ions is reacted, and then a fluoride ion solution containing is added or a chloride of a divalent metal containing solution is reacted with a solution containing phosphate ions, and then a solution containing activator ions and fluoride ions is added or a solution containing a chloride of a divalent metal with a Fluoride ions containing solution is reacted, and then a phosphate ions and activator ions containing solution is added. 14. The method according to claim 12, characterized in that a precipitated apatite matrix for introducing activator ions with one of these containing solution is brought together. 15. The method according to any one of claims 12, 13 or 14, characterized gekennzeiclinet1 that then the product obtained is thermally treated. 16. The method according to any one of claims 4 to 15 for producing a calcium-containing alkaline earth metal halophosphate fluorescent mass @ by precipitation at elevated temperature, characterized in that the precipitation occurs at a temperature is carried out at a maximum of 56 oC.