DD302011A9 - Glassy or glassy-crystalline material with fast solubility and process for its preparation - Google Patents

Abstract

A vitreous or vitreous-crystalline, rapidly dissolving material has the following composition (wt.%) before combustion: 20 - 55 CaO, 5 - 25 Na2O, 0.01 - 15 K2O, 0 - 15 MgO, 30 - 50 P2O5, 0 - 15 SiO2, 0 - 40 Na2SO4 and/or K2SO4. The new material can be obtained in vitreous or vitreous-crystalline form, depending on the cooling conditions. As a spontaneously crystallized glass ceramic, it contains the rhenanite phase, ''A'' phase, ''X'' phase and/or their mixed crystals. The material is both bioactive and biocompatible and dissolves rapidly. It can be used directly and with other materials as an implant for temporary bone replacement and to induce growth of connective tissue, and as a fertilizer and fodder material.

Description

Field of application of the invention

The invention relates to methods of preparation of materials which are defined to be rapidly soluble and release no toxic substances with respect to their use. They can be used wherever defined solution rates are necessary in a wide range, such as in the application as a bone substitute, Bin Jegewebesubstitut, in the connective tissue induction, as a carrier material for inorganic components such. B. trace elements, feed additives or fertilizers.

Characteristic of the known state of the art

Materials having extremely fast solubility are known in the art by considering naturally occurring or synthetically produced salts. This applies both to the field of fertilizers and animal feed etc. as well as to the field of application of bone ice. However, the extremely rapid release of all components often produces an unphysiological, even partially toxic concentration ("over-fertilization") of inherently physiological constituents, and a further disadvantage is that these substances do not give off any depot effect In the bone or connective tissue substitution, such simple salts have also not proven useful.To remedy this disadvantage in the medical field in question so-called resorbable bone substitutes based on tricalcium phosphate or hydroxyapatite have been introduced, their resorption time is again too long in many applications.

Technical solutions for the fertilizer sector, which include a depot effect for this application, are based on materials that have very high phosphate contents and can be classified as metaphosphate glasses (see: Knott, P., Glasses-Agricultural applications, Glastechn. Ber. 62 [1989] 1,29-34; GB-F 2 099 702 A). This also applies to feed, but especially to materials that can be subcutaneously implanted in livestock production, although in this case the solutes are preferably used as carrier materials to compensate for deficiencies, particularly magnesium, copper, cobalt and / or Selenium.

Again - as in the case of fertilizers - is the high phosphate content, due to the choice of metaphosphate glasses disadvantageous (see this: Harenz, H., phosphorus use and phosphorus losses in agriculture - nutrition - budget of the GDR from an economic and environmental point of view , From Arb. Plenum Kl. AdW GDR - Berlin 14 (1989J3., 25-43) In the field of bioactive bone replacement materials, as already mentioned, resorbable materials are used only in the field of calcium orthophosphates, their originally low solubility by Various chemical and mechanical processes can be varied within certain limits (Vergi on this: Bauer, G, Hohenberger, G .: Causes of different behavior of bioactive calcium phosphate ceramics in the organism, cfi / Ber. DKG 66 [198911/2 , 23-27.)

EP 0 237 043 describes the preparation of calcium phosphate-containing biocompatible laminates, the basic body having a layer which allows a higher calcium release than the main body itself. Other solutions expressly refer to the ion donor effect of both calcium ions and magnesium ions. , Sodium and potassium ions. In DE 2 346 739 a sintered product of apatite, glass / vitreous and perrnutite for use as implant material is described from this point of view.

The bioactive materials of CaO-P ₂ O ₆ -SiO ₂ -TyP described in DD 248 351 and DE-OS 3 306 648 show, in granulated form, a stronger release of calcium, sodium, potassium and magnesium ions, but they do so At the same time, larger amounts of silicon released, so that use of these materials is possible only in a compact form. So far, no material has been developed with a defined fast solubility that covers just the area that on the one hand guarantees a depot effect on fertilizers and the above-mentioned subcutaneous implantation in animal production and on the other hand overcomes the (still) too low resorption capacity of bone substitute materials helps. This material should be from the perspective of fertilizers as well as the bone substitute materials, etc. have not zi ¹ high levels of phosphorus, as is inherent in the metaphosphate glasses. Nevertheless, the material should be readily fusible and pourable, which represents a further advantage, in particular with regard to the processability and the homogeneity of the product.

Object of the invention

It is the object of the invention to overcome the geschildei th disadvantages of the prior art.

Essence of invention

The invention has for its object to provide a material which is rapidly soluble both defined in and ex vivo and can be melted well, shed and produced in granular form.

According to the invention, a material with these features has been developed, which moreover has further advantageous properties, which are described in more detail below.

Melting the mixture of the composition (in parts by mass in%):

22-43 CaO

8-20 Na ₂ O

0-14 K2O, preferably 0.1-14;

0-15 MgO, preferably 0.1-15; 30-55 P ₂ O ₅

0-15 SiO ₂ , preferably 0.1-15;

0-40 Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-35

a, sheds or frits them, one obtains spontaneously crystallized glass-ceramics, which surprisingly contain a so far in the ASTM file and in the relevant literature not designated crystalline phase, which is referred to in the context of this description with "X", or obtained Mixed crystals of this phase "X".

By X-ray diffractometry this phase becomes "X" or mixed crystals of this phase are roughly characterized by the following d-values and intensities:

2,885 90 2,717,100 2,552 10 2,351 10 2,239 20 2,164 8 1,980 40 1,827 8 1,597 10 -4 - 302 011 3,199 8 2,851 90 2,679,100 2,529 10 2,321 10 2,209 20 2,141 8 1,953 40 1,808 8 1,578 10 1,569 10 1,517 10 3.189 δ 2,844 90 2,667,100 2,523 10 2,310 10 2,199 20 2,135 8 1,945 40 1,804 8 1,571 10 1,547 10 1,498 10 3,15 8 2,835 90 2,663,100 2,514 10 2.303 10 2,195 20 2,131 8 1,941 40 1,800 8 1,569 10 1,539 10 1,495 10 3:12 8 1,537 8 1,491 8

Composition example cd value: 3.945 3.650 3.384

Intensities: 20 20 2

Composition ¹ is a d value: 3.904 3.618 3.347

Intensities: 20 20 2

Composition example d d value: 3.892 3.611 3.333

Intensities: 15 20 2

Composition Example b d value: 3.875 3.600 3.325

Intensities: 20 20 2

This crystalline phase is thus similar to the phase referred to in the literature as phase "A" (see, for this: Ando, J. Matsuno, S .: Ca ₃ (PO ₄ Ij-CaNaPO ₄ System, Bulletin, Chem 41 [1968] 342-347), but differs from them by significant line shifts and intensity changes as well as the absence of a strong diffraction line at the New Plane (421). "A" has been described by Ando as a superstructure of the hexagonal calcium sodium orthophosphate. where he designates both the high and the low temperature form of CaNaPO * as alpha- and beta-rhenanite, respectively, and the mere formulation rhoanite thus includes both forms. This usage of language or this definition of rhenanite is followed in the present description.

The structural type of "A" is also the phase "X" attributable, allom apparently to over half of the sodium can be replaced by potassium and also calcium can be partially substituted by magnesium in this structure. These substitutions are generally referred to herein as mixed crystal formation.

The materials containing this phase now also show the desired properties with regard to a defined rapid solubility, in particular with regard to the bone substitution. In animal studies, it has also surprisingly been found that a certain part of these substances in turn induces connective tissue formation

 The new materials are in the cooled state at room temperature as a glass or glass crystalline material, but can in principle be converted into the glass crystalline state and have essentially physiological constituents. The rate of dissolution of the materials, according to the application, is adjusted within wide limits, as described in more detail below, so that no toxic reactions or overconcentrations of any components are implied.

An expansion of the melting range leads beyond the "X" phase to further crystalline phases which are known per se. "Phase A" or its mixed crystals, rhenanite or its mixed crystals can additionally or individually be present in the material produced according to the invention his. These compositional variations are also suitable for application in genannton applications in terms of the objective, as well as the inclusion of the known isomorphism of the sulfates of potassium and sodium. This extended composition area thus extends to the already mentioned components in their mass fractions in%:

20-55 CaO 5-25 Na ₂ O 0.01-15K ₂ O 0-15MgO 30-50P ₂ O ₆ 0-15SiO ₂ 0-40 Na ₂ SO ₄ and / or K ₂ SO ₄ .

However, a further increase in the Calciumorthophosphatanteilö leads to increasingly heavier or non-meltable and non-pourable materials, thus approaching both of their manufacturing process as well as in their properties (solubilities) dün known materials or move away from the objectives of the present invention

 Particularly advantageous embodiments are therefore in the concentration ranges (mass fractions in%)

21-50 CaO, in particular 23-50 5-20 Na ₂ O, in particular 6-20 0.1-14 K ₂ O, in particular 2-14 0.1-12 MgO, in particular 0.5-10

32-48 P ₂ O ₆ , in particular 35-48 0.1-15 SiO ₂ , in particular 1-10 0.1-35 Na ₂ SO ₄ and / or K ₂ SO ₄ , in particular 0.1-20.

Another preferred embodiment of the material according to the invention consists of

22-55 CaO, 6-12 Na ₂ 0.3-14 K ₂ 0.2-8 MgO, 37-43 P ₂ O ₆ , 0.5-10 SiO ₂ , 0.5-20 Na ₂ SO ₄ and / or K ₂ SO ₄ .

The erfindungsgsmäße material is further characterized in that it can be converted at a temperature in the range of 1200 ⁰ C to 1550 ³ C in a pourable melt. Another characteristic of the material is that the melt at a cooling rate of greater than about 150 ⁰ C per minute in the glassy state at room temperature

can be transferred and that the melt spontaneously crystallized on cooling at normal cooling rate or at a cooling rate which is slower than about 35 ° C per minute. This forms a fine crystalline structure.

Furthermore, it has been found that spontaneously crystallized material of the same chemical composition as the corresponding Glos (obtained under extreme cooling conditions) or the crystalline material produced from the glass by tempering each have different solubilities. It has furthermore been found that the spontaneously crystallized glass-ceramic as crystalline main constituents at least one of the phases of Rhenanits, mixed crystals of Rhenanits, the phase "A", mixed crystals of the phase "A", the above-mentioned new phase "X" and / or mixed crystals contains the phase "X". The material may additionally contain glaserite and / or crystalline potassium sulfate.

If the main crystalline constituents of the material are rhenanite or mixed rhenanite crystals, the composition of the material in the mixture is as follows (in% by mass and calculated on an oxide basis):

30-40 CaO; 15-20 Na ₂ O; 0-1 K ₂ O, preferably 0.01-0.1 K ₂ O; 0-5 MgO, preferably 0.1-5 MgO; 40-55 PjO ₆ ; 0-15 SiO ₂ , preferably 0.1-8 SiO ₂ ; 0-30 Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-25 Na ₂ SO ₄ and / or K ₂ SO ₄ .

By "main crystalline constituent" is meant that the percentage of the component is higher than the proportion of other components present in the material.

If the material contains the phase "A" as the main crystalline constituents, the composition of the material in the mixture is as follows (calculated in% by mass and calculated on an oxide basis):

40-50 CaO; 8-20 Na ₂ O; 0-1 K ₂ O, preferably 0.1-1 K ₂ O; 0.5 MgO, preferably 0.1-5 MgO; 40-50 P ₂ O ₆ ; 3-20 SiO ₂ ; 0-30 Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-25 Na ₂ SO ₄ and / or K ₂ SO ₄ .

If the material contains the phase "X" or mixed crystals of the phase "X" as main crystalline constituents, the composition of the material in the mixture is as follows (in parts by mass in% and calculated on an oxide basis):

22-45 CaO; a-20 Na ₂ O; 0-14 K ₂ O, preferably 0.1-14 K ₂ O; 0-15 MgO, preferably 0.1-15 MgO; 30-55 P ₂ O ₆ ; 0-15 SiO ₂ , preferably 0.1-15 SiO ₂ ; 0-40 Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-35 Na ₂ SO ₄ and / or K ₂ SO ₄ .

A particular advantage of the invention is that the material is biokumpatibei, sometimes even bioactive in the sense of a direct Knochenanlagerung or under constant release allows the formation of new bone tissue. On the other hand, it also promotes connective tissue formation. The material can be used for example as granules with a grain size in the range of

The invention further provides a process for the preparation of a glassy or glassy crystalline material having a fast solubility, which comprises reacting a mixture consisting of (in% by mass and based on oxide):

20-55 CaO; 5-25 Na ₂ O; 0-15 K ₂ O; 0-15 MgO; 30-55 P ₂ O ₆ ; 0-15 SiO ₂ ; 0-40 Na ₂ SO ₄ and / or K ₂ SO ₄

melts for at least 10 minutes at a temperature of about 1200 to 1 580 ° C and the melt cools. Preferably used are the preferred compositions already mentioned above.

As already stated above, the cooling can be carried out with a very high cooling rate of at least 150, but better 5 * 10 ^2o C per minute while a glassy material can be obtained.

However, the main route to the production of rapidly soluble materials according to the invention consists in melting with subsequent spontaneous crystallization. Therefore, in the further all embodiments should preferably be aligned with this procedure. The melt is cooled at a rate of less than about 35 ⁰ C per minute, wherein the spontaneous crystallization occurs. Advantageously, the spontaneously crystallized material is subjected to a conventional tempering process. This is carried out in the temperature range of about 600 to 1200 ⁰ C, depending on the chemical composition and the crystal phase to be generated in order to increase the crystalline content - usually it is the crystalline main phase - even further. The relationship between chemical composition and crystal phase has already been generally described above. It occur through the treatment according to the invention, the crystal phases of rhenanite, the phase "A", mixed crystals of the phase "A", the phase "X", mixed crystals of the phase "X", glaserite and / or crystalline potassium sulfate in appearance.

It is advantageous for the process according to the invention to use P ₂ O ₆ in the form of phosphoric acid.

An advantageous material form is the granular form, so that the cooled and optionally tempered material is comminuted and classified by conventional methods.

When the content of Na ₂ SO ₄ and / or K ₂ SO _{4 is} about equal to or more than 3 mass% in the starting mixture, it is advantageous to add the granules to a treatment with distilled water over a period of 0.1 to 10 hours elevated temperature, preferably at about 80 to 100 ⁰ C suspend. As a result, an increase in the inner surface of the material is achieved, which is expressed in an increase in the solubility, and the Suifatanteil can, if it is not desired, can be reduced. In addition, the sulfate recovered in this way can be recycled to the processing process.

As already stated, the Neua rapidly soluble material can be used as a resorbable bone substitute material or for connective tissue induction.

It is expedient to granules in the desired grain size in the corresponding body region 6n, z. As postoperative cavities in the human or animal body to bring, this being done in admixture with other substances may, for. B. with less rapidly soluble biocompatible materials. DD 258 713, carrier foils, etc. When used for the induction of connective tissue, the concrete composition selected first determines the success of the treatment; however, mixtures with other substances known to result in no bone attachment may also be used in this case.

The material can also be used to coat implants for hard tissue replacement, consisting of metals or alloys and / or ceramics, preferably Al ₂ O ₃ -coramates, so that it would contribute to an improved and, above all, faster healing phase.

It has furthermore been found that the materials according to the invention having rapid solubility in the composition described at the outset, including the advantageous composition ranges, can be used particularly successfully as fertilizers. Compared to conventional fertilizers, they have a reduced phosphate content and are advantageous because of their delayed release of phosphate for almost all applications. The problem of "over-fertilization" can hardly occur with the materials according to the invention.On the basis of good meltability and pourability, easily finely grindable end products can be produced without much effort Nitrogen carriers are combined and introduced by known methods as dust (suspension) or granules on or in the soil.

Suitable trace nutrients for fertilizers in the material according to the invention are the following micronutrients: boron, copper, manganese, zinc, iron, cobalt, molybdenum. The fertilizers according to the invention are particularly suitable for intensively cultivated soils, as they are particularly lacking in potassium, phosphorus and magnesium, and sometimes also in sulfur.

Since it is customary to use sulfur as so-called "topical fertilizer", the form present in the material according to the invention counteracts the use of sulfur, the possibility of rapid release, in particular of sulfur-containing potassium component, in the case of implantation of such materials in living organisms to use the sodium component preferably).

The application as a fertilizer concentrates on allotments, vineyards and fruit, but it would also be favorable for field beans and rye, since comparatively much calcium is removed from the soil and calcium-rich fertilizers are also derivable from the composition field according to the invention.

Although preferably only basic fertilizer is applied before sowing, it is also advisable to apply the depot fertilizer according to the invention. The quantities to be applied can be determined on the basis of the respective soil analysis in connection with the tested solubilities of the materials (see also the analysis values of the rapid method for the determination of the solubility below).

It has furthermore been found that the materials according to the invention having rapid solubility in the composition described at the outset, including the advantageous composition ranges, can be used successfully as a feed additive. Compared to conventional Futtermittebusatz based on metaphosphate glasses are achieved by reduced but sufficient phosphate content, which is slowly implemented in the animal body, beneficial effects.

Particularly favorable is the shape of the subcutaneous implant body, which additionally contains the trace elements such as copper, cobalt and / or selenium in the desired amount, d. h., the concentration of these components may well include higher percentages in the implant body.

The feedstuffs according to the invention may furthermore contain customary excipients and / or carriers as well as known feedstuffs in useful admixtures. They may be administered as pellets or in suspension in a liquid diet; however, they can advantageously be used in the abovementioned subcutaneous implant body shape and thus specifically for the treatment of gastric symptoms in Tior production. The application rates can be roughly determined according to the requirements from the solution experiments given below. However, the higher the trace element addition is chosen, the more the changed (delayed) solution mechanisms occur, which must be taken into account in corresponding estimates.

In order to be able to compare the in vitro solubility of various substances, two different ways have been identified, one being the solubility in a differential circulation cell and the other a rapid method to be noted here:

The material to be examined is comminuted and the selected for the determination of grain fraction of 315-400 pm is removed. The sample material is washed with ethanol and then dried at 110.degree. 10 samples of approximately 2 g each of the test substance are weighed on the analytical balance. Bidistilled water is heated to 37 ⁰ C and 200ml each in the beaker are mixed with the weighed about 2g. This sample remains in the incubator for 24 h at 37 ⁰ C, covered with a watch glass, stand. After this time, the samples are quantitatively transferred to pre-weighed fries.

Thereafter, the filters are dried with the sample substance at 11O ⁰ C. After cooling in the desiccator, the new weighing is carried out to determine the weight loss according to: (weight in mg-weight in mg) * 1000 / weight in mg = result in mg deadweight loss / g weight

Then the standard deviation is calculated.

The following values result from this method:

Material or Batch 1 mg loss of substance / g weight Material code ") Lot qe? Ca ₃ (PO ₄ I ₂ Batch '· 3.1 ± 0.39 Charge4 3.0 ± 0.63 Batch 1 2.9 + 0.60 Batch 1 2.2 ± 0.16 4CaO * P ₂ O ₆ Batch 2 1.8 ± 0.72 a Batch 3 5.9 ± 0.27 6.6 ± 0.55 6.2 ± 0.28 b Batch 1, untreated 5.7 ± 0.84 C Batch 2, untreated 14.7 ± 0.77 d Lot 1, treated 93.6 ± 3.57 untreated 87.6 ± 1.22 bohandelt 23.1 ± 1.23 e (glassy, quenched) 36.6 ± 1.68 3.8 ± 0.77 f Lot 10, untreated 54.9 ± 7.12 G Lot 10, untreated 9.8 ± 1.98 O 188.0 ± 0.99 (n = 5) P 244.9 ± 0.5 (n = 6j

') Compositions see Table 1

According to the results of the rapid method of determining the solubility, it is clear that a coarse division of the materials can be made after the main crystal phases:

Rhenanite or mixed crystals of rhenanite about 3 ... 10 mg / g

Phase "A" or mixed crystals of phase "A" about 1 ... 4 mg / g phase, X "or mixed crystals dor phase" X "about 7 ... 15 mg / g.

With the addition of the sulphate components or after carrying out a corresponding treatment (leaching) of materials with high sulphate oantiles, this classification is of course no longer valid; these values were then exceeded as desired.

However, it is generally found that in particular materials containing the (new) phase "X" or mixed crystals of the "X" phase are particularly suitable for the preparation of the pure and sulfated mixed melts and products derived therefrom. This expresses u. a. in the good pourability of the melts, the homogeneity of the materials, the leaching ability in the presence of sulfates, etc. from.

embodiments

The preceding embodiments, which can be seen only the full scope of the invention, wei explained in more detail below by a few examples. The mixtures mentioned in Table 1 were melted and comminuted according to the following application tests. The crystalline phases were determined, the solubility tested by the described rapid method and in the differential circuit. Some of these results have already been presented in the preceding section

 In the following, examples will be given of some examinations with regard to the application.

Table 1 - List of Assay Examples:

Code oxide composition in% by mass

Name CaO MgO Na ₂ OK ₂ O

P ₂ O ₆

SiO,

additions

a 24.0 5.4 8.3 13.3 40.1 8.9 _ b 25.11 5.52 13.70 6.94 41.48 7.38 - C 31.5 - 8.3 13.3 40.1 8.9 - d 24.0 5.4 8.3 13.3 40.1 8.9 10Na ₂ SO ₄ e 25.11 5.52 13.70 6.94 41.48 7.38 10Na ₂ SO ₄ f 26.63 6.04 9.27 14.12 34.05 9.05 - G 18.68 6.73 10.32 15.64 38.63 10.00 H 25.76 4.64 11.27 17.48 40.85 - - i 25.76 4.64 11.27 17.48 40.85 - 8Na ₂ SO ₄ j 32.75 - 13.7 6.94 41.48 7.38 - k 32.75 - 13.7 6.94 41.48 7.38 4 Na ₂ SO ₄ I 24.35 5.52 8.84 13.54 40.54 7.21 - m 24.35 5.52 8.84 13.54 40.54 7.21 4K ₂ SO ₄ η 24.35 5.52 8.84 13.54 40.54 7.21 10K ₂ SO ₄

Continuation of Table I

Code oxide composition in% by mass

Name CaO MgO Na ₂ OK ₂ OP ₂ O ₆ SIO ₂ Additions

O 24.35 5.52 8.84 13.54 40.Ü4 7.21 30 Na ₂ SO ₄ P 24.0 5.4 8.3 13.3 40.1 8.9 20Na ₂ SO ₄ q 24.0 5.4 8.3 13.3 40.1 8.9 10 Na ₂ SO ₄ and 10K ₂ SO ₄ r 24.35 5.52 8.84 13.54 40.54 7.21 4.5 Na ₂ SO ₄ and 4.5 K ₂ SO ₄ S 25.76 4.64 11.27 17.48 40.85 - 3 Na ₂ SO ₄ and 18K ₂ SO ₄

example 1

A material of composition g was comminuted after melting and cooling under normal conditions. A particle fraction of 200 to 500 μm was selected for the subsequent animal experiments.

The material was implanted both subcutaneously and in the bones of rats and rabbits. After 4.8 and 12 weeks of storage time, the material was still detectable in both cases, although the proportion or grain size had decreased considerably. In the bone tissue, the material was directly contacted by bone tissue, whereas in the subcutaneous implantation a strong connective tissue involvement had been implicated.

Example 2

A material of composition f was melted, cast into a plate, and crushed in the oven after slow cooling. The granules of the grain fraction from 200 to SOOpm were implanted analogously to Example 1.

Histological examination revealed that the material, like all implanted materials, healed inflammatory. In this case, it was further shown that the material was completely absorbed in the bone tissue after 12 or 20 weeks. On the other hand, particle residues in the connective tissue could be detected after subcutaneous implantation.

Example 3

Analogously to Example 2, material of composition a was produced and implanted. While remnants of the implanted granules were still detectable in the bone after 15 weeks, it had already been completely absorbed in the subcutaneous tissue after this time.

Example 4

A material of composition d was melted at 1500 ° C, cast into a plate, which was then crushed after cooling. The granules of the grain fraction of 200-500 μm produced therefrom were pretreated once,

ie, at 90 ⁰ C for 30 min in dist. Boiled water, and, otherwise untreated, implanted in experimental pigs in the bones.

After 20 weeks of storage, both materials were completely resorbed. However, no bone formation has been implicated in these sites, which makes the material suitable for filling cavities where connective tissue is to be induced.

Example 5

The material production and the animal experimental testing was carried out exactly according to Example 4.

In both cases, however, 55% by weight of the material according to the invention was mixed with 45% by weight of a surface-modified tricalcium phosphate (TCP) granulate (corresponding to WP-DD 258 713 A 3) and implanted.

In these cases, bone formation was found in the artificially set defects, although remnants of TCP were still detectable after this period of 20 weeks. However, these implant residues are comparatively extremely low in the case of filling the bone defects with pure surface-modified TCP.

By this combined application, the bone is fully functional after a corresponding healing phase.

Claims (27)

1. A glassy or glassy-crystalline material having rapid solubility, characterized in that the mixture before firing the material has the following chemical composition (in parts by mass in% and calculated on an oxide basis) 20-55% CaO 5-25% Na ₂ O
0.01-15% K ₂ O 0-15% MgO
30-50% P ₂ O ₅ 0-15% SiO ₂ 0-40% Na ₂ SO ₄ and / or K ₂ SO ₄ . 2. Material according to claim 1, characterized in that it consists of 20-55% CaO, preferably 21-50, in particular 23-50 5-25% Na ₂ O, preferably 5-20, in particular 6-20 0.1-15% K ₂ O, preferably 0.1-14, in particular 2-14 0.1-15% MgO, preferably 0.1-12, in particular 0.5-10 30-50% P ₂ O ₅ , preferably 32-48, in particular 35-48 0.1-15% SiO ₂ , preferably 2-15, in particular 3-15, 0.1-35% Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0, i-20, in particular 0.1-15. 3. Material according to claim 1 or 2, characterized in that it consists of 22-50% CaO; 6-12% Na ₂ O; 3-14% K ₂ O; 2-8% MgO; 37-43% P ₂ O ₆ ; 0.5-10% SiO ₂ and 0.5-20% Na ₂ SO ₄ and / or K ₂ SO ₄ . 4. Material according to any one of claims 1,2 or 3, characterized in that it can be converted at a temperature in the range of 1200 to 1550 ⁰ C in a pourable melt. 5. Material according to claim 1 to 4, characterized in that the melt can be converted into the glassy state at room temperature due to a cooling technique, which allows a cooling rate of greater about 5 · 10 ² ° C per minute. 6. Material according to claim 1 to 4, characterized in that the melt spontaneously crystallized on cooling at normal cooling rate or at a cooling rate which is slower than about 35 ⁰ C per minute. 7. Material according to claim 1 to 4 and 6, characterized in that the spontaneously crystallized glass ceramic as crystalline main components at least one of the phases of rhenanite, mixed crystals of rhenanitol, the phase "A", mixed crystals of the phase "A", the phase "X" and / or mixed crystals of the phase "X". 8. Material according to claim 7, characterized in that it additionally contains glaserite and / or crystalline potassium sulfate. 9. Materials according to claim 1 to 4 and 5 to 8, characterized in that are present as crystalline main components Rhenanit or mixed crystals of Rhenanits having the following chemical composition (in mass fractions in% and calculated on an oxide basis): 30-40% CaO; 15-20% Na ₂ O; 0-1% K ₂ O, preferably 0.01-0.1%; 0-5% MgO, preferably 0.1-5%; 40-55% P ₂ O ₅ ; 0-15% SiO ₂ , preferably 0.1-8.0%; 0-30% Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-25. 10. Material according to claim 1 to 4 and 6 to 8, characterized in that there are present as crystalline main constituents the phase "A" or mixed crystals of the phase "A", which have the following chemical composition: 40-50% CaO; 8-20% Na ₂ O; 0-1% K ₂ O, preferably 0.1-1%; 0-5% MgO, preferably 0.1-5%; 40-50% P ₂ O ₅ ; 3-20% SiO ₂ ; 0-30% Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1 to 25%. 11. Material according to claim 1 to 4 and 6 to 8, characterized in that as crystalline main constituents the phases "X" or mixed crystals of the phase "X" are present, which have the following chemical composition: 22-45% CaO; 8-20% Na ₂ O; 0-14% K ₂ O, preferably 0.1-14%; 0-15% MgO, preferably 0.1-15%; 30 to 55% P ₂ O ₅ ; 0-15% SiO ₂ , preferably 0.1 to 15%; 0-40% Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-35%. 12. Material according to claim 1 to 4, characterized in that the glassy or glass-crystalline material is biocompatible. 13. Material according to claim 1 to 12, characterized in that it is bioactive in the sense of a direct Knochenanlageriing or unterständigem release allows the formation of new bone tissue. 14. Material according to claim 1 to 12, characterized in that in the mixture with alpha-tricalcium phosphate and / or hydroxyapatite is present. 15. Material according to claim 1 to 14, characterized in that it is present as granules of grains in the range of 63 to 5000 microns. 16. A process for the preparation of a glassy or glass-crystalline material with rapid solubility, characterized in that a mixture consisting of (in% by mass and calculated on an oxide basis) 20 to 55% CaO; 5 to 25% Na ₂ O; 0 to 15% K ₂ O; 0 to 15% MgO; 30 to 50% P ₂ O ₅ ; 0 to 15% SiO ₂ ; 0 to 40% Na ₂ SO ₄ and / or K ₂ SO ₄ melts for at least 10 minutes at a temperature of 1200 to 1580 ⁰ C and the melt cools. 17. The method according to claim 16, characterized in that the mixture consists of 20-55% CaO, preferably 21-50, in particular 23-50 5-25% Na ₂ O, preferably 5-20, in particular 6-20 0.1-15% K ₂ O, preferably 0.1-14, in particular 2-14 0.1-15% MgO, preferably 0.1-12, in particular 0.5-10 30-50% P ₂ O ₅ , preferably 32-48, in particular 35-48 0.1-15% SiO ₂ , preferably 2-15, in particular 3-15 0.1-35% Na ₂ SO ₄ and / or K ₂ SO ₄ , preferably 0.1-20, in particular 0.1-15. 18. The method according to claim 16 or 17, characterized in that the mixture consists of 22-50% CaO; 6-12% Na ₂ O; 3-14% K ₂ O; 2-8% MgO; 37-43% P ₂ O ₅ ; 0.5-10% SiO ₂ ; and 0.5-20% Ma ₂ SO ₄ and / or K ₂ SO ₄ . 19. The method according to claim 16 to 18, characterized in that one cools the melt at a rate less than about 35K per minute, wherein the material crystallizes spontaneously. 20. The method according to claim 16 to 19, characterized in that the spontaneously crystallized material is subjected to a conventional annealing process in the temperature range of about to 1 200 ⁰ C, depending on the chemical composition to further increase the crystalline content, wherein the Crystal phases of rhenanite, mixed crystals of rhenanite, the phase, .A ", mixed crystals of the phase" A ", the phase" X "mixed crystals of the phase" X ", glaserite and / or crystalline potassium sulfate appear, but usually the proportion the main crystal phase is further increased. 21. The method according to claim 16 to 18, characterized in that one cools the melt at a rate greater than about 5 · 10 ² K per minute and the material is consequently glassy at room temperature. 22. The method according to any one of claims 16 to 18, characterized in that the P ₂ O _{6 is used} in the form of H ₃ PO ₄ . 23. The method according to one or more of claims 19 to 21, characterized in that the cooled material is brought by comminution and classification in a granular form. 24. The method according to claim 23, characterized in that the granules of a treatment with distilled water over a period of 0.1 to 10 hours at elevated temperature, preferably at about 80 to 100 ⁰ C, exposed when the content of Na ₂ SO ₄ and / or K ₂ SO _{4 is} approximately equal to or greater than 3 mass fractions in% Ausgangsτι initial amount. 25. Use of the material according to claim 1 to 15, characterized in that it is used as a resorbable bone substitute material. 26. Use of the material according to claim 1 to 15, characterized in that it is used for Bindegewebsinduktion. 27. Use of the material according to claim 1 to 15, characterized in that it is used as a coating material for implant moldings for hard tissue replacement, consisting of metals or alloys and / or ceramics, preferably Al ₂ O ₃ ceramics.