SINTERED APATITE BODIES AND COMPOSITES THEREOF

Abstract: There are provided a novel sintered apatite body and a novel sintered apatite-mineral fiber material composite. The crystals of the sintered apatite have fine dense crystalline structures comprising needle-like fine crystals and are entangled together, whereby the mechanical properties of the sintered apatite body or composite are markedly en­ hanced. The sintered body and composite wherein the apatite is hydroxyapatite are useful for bioceramic uses. The sintered apatite body or composite is produced by baking under pressure an apatite material alone or in contact with a reinforcing mineral fiber material in the presence of water at a temperature lower than 1000°C, and further at a tempera­ ture lower than the temperature causing deterioration of the fiber material in the case of the composite.

Description: SINTERED APATITE BODIES AND COMPOSITES THEREOF This invention relates to a sintered apatite body comprising needle-like crystals and a sintered apatitemineral fiber material composite. More particularly, this invention relates to a process for producing a sintered apatite body and a sintered composite consisting essentially of a matrix amount of an apatite and an effective amount of a reinforcing mineral fiber material, as well as the resulting sintered apatite-mineral fiber material composite. The process for sintering is characterized by baking an apatite material at a defined, relatively-low temperature under pressure in the presence of water. Apatite materials for sintering are typically represented by hydroxyapatite, carbonate-apatite, fluoroapatite and chloroapatite. Processes have been proposed hitherto for'sintering these apatites and especially hydroxyapatite by a hot press at high temperatures of about 11000C or higher in the absence of water. These sintered hydroxyapatite products, however, had a variety of serious problems such as poor mechanical strength properties (especially, impact strength and bending strength? due to their crystalline structures, large pores or flaws, and the like. For example, refer to R.W. RICE et al., J. Am. Ceram. Soc., 63 (3-4), (1980) 129-136, and T. KIJIMA et al., J. Am. Ceram. Soc., 62, (9-10) (1979) 455-460. These sintered apatite products were expected to be useful for broad applications such as ceramic materials, electronic materials, filter materials, bioceramics (e.g., artificial bone and tooth implants) and the like, but it can not be said that they have ever been success fully utilized in these uses because of their inadegnate mechanical properties, etc. Attempts to reinforce sintered apatite with reinforcing materials such as fibers would naturally be considered by those skilled in the art. These attempts, however, have been impeded by the following fundamental problems; (i) sintered apatite bodies baked at such high temperatures are rather brittle and weak in mechanical strength, and thus reinforcement with such fiber materials is not so effective, and (ii) most of such reinforcing materials deteriorate markedly in mechanical strength under the conventional baking conditions of 11000C or higher for sintering apatite-reinforcing material composites. In accordance with conventional technical ideas for producing a sintered apatite, it has been considered that the satisfactory sintering of a pure apatite material containing no additive compound is substantially impossible at a temperature lower than 11000 or 10000C and especially lower than 8000C, or that, even when the apatite could be narrowly sintered at such low temperatures, the physical properties of the resulting sintered apatite are inevitably reduced to the point of uselessness. In this connection, the present inventor has surprisingly found that apatite can be sintered under pressurization at a temperature lower than 10000C and preferably lower than about 8000C in the presence of water to produce a sintered apatite body having far superior mechanical properties and uniform porosity in comparison with conventional sintered apatite. In addition to his intensive investigations into sintered apatite products resulting in the above mentioned invention, the inventor also made intensive investigations into a sintered apatite-reinforcing fiber material composite to further enhance its mechanical properties. Initially the present inventor used glass fibers and iron fibers which are normally excellent as reinforcing materials and readily available at low cost, but the expected increase in mechanical properties was not observed with respect to sintered apatite composites baked at about 7000C. The inventor presumed that the problems were due to the deterioration of the fiber materials under oxidizing atmospheres, even at about 7000C, and also due to the chemical affinity of the fiber materials with apatite at such a temperature. The inventor therefore tried to produce apatite-fiber composites wherein glass fiber or carbon fiber was used as reinforcing material at baking temperatures lower than 400 C and 5000C, respectively, and unexpectedly succeeded in producing apatite composites having excellent properties. The full reasons for the above-mentioned phenomena have not yet been fully clarified. It is conjectured, however, that glass fiber or iron fiber has physical and chemical affinity with apatite at a baking temperature of about 7000C and thus the reinforcing fiber is deteriorated and also firmly bonded to the sintered apatite, whereby a sliding action between the fiber and sintered apatite is lost and the resulting composite is readily broken by a force applied thereto. However, the reinforcing fiber materials to be used in the present invention have sufficient physical affinity with apatite but are completely or substantially inert from the viewpoint of chemical affinity with apatite at a baking temperature of the present invention. Thus, it can be conjectured that an apatite-reinforcing fiber composite having excellent mechanical properties, and especially impact and bending strength properties, can be unexpectedly obtained1 because some sliding actions between the fiber material and sintered apatite are present in composites according to the present invention. Incidentally, this is rather surprising in view of the fact that, in conventional resin-fiber composites consisting of fiber materials and synthetic resins, the bonding affinity between the fibers and resins (for example by using a bonding accelerator) is desired and taken seriously, but the problems as raised above seem different in the case of-sintered apatite-mineral fiber composites because in the case of the resin composites the resin itself has some flexibility and the like. instead of the above mentioned sliding actions. It is an object of the invention to provide a process for producing a novel sintered apatite body and a novel sintered apatite-mineral fiber material composite. It is another object of the invention to provide a novel sintered apatite body and a novel sintered apatitefiber material composite having broad ranges of applications by utilizing their excellent properties. Further objects of the present invention will become apparent from the following description. In accordance with the present invention, there is provided process for sintering apatite, which comprises baking an apatite material selected from hydroxyapatite, carbonate-apatite, fluoroapatite, chloroapatite, precursor materials thereof, and mixtures thereof, characterized by baking the apatite material in the presence of water in addition to the crystal water thereof under pressure at a temperature lower than 10000C and preferably lower than 8000C to substantially sinter the apatite material. Preferably, a matrix amount of the apatite material is baked in contact with an effective amount of a reinforcing mineral fiber material at a temperature lower than 10000C and lower than the temperature causing substantial deterioration of the fiber material. Further in accordance with the present invention, a sintered apatite composite comprising a reinforcing material and a sintered apatite matrix wherein the apatite is selected from hydroxyapatite, carbonate apatite, fluoroapatite, chloroapatite and mixtures thereof 1 consists essentially of an effective amount of a reinforcing mineral fiber material and a matrix amount of sintered apatite in contact with the fiber material, the crystals of the sintered apatite having fine dense. crystalline structures comprising at least about 30% by weight of needle-like fine crystals and are entangled together and the fiber material is not substantially deteriorated. Thus, novel sintered apatite bodies are provided having fine dense polycrystalline structures wherein the crystals comprise or consist essentially of straight and/or curved needle-like crystals and are entangled together, which exhibit excellent physical properties, as well as a novel sintered apatite-mineral fiber material composite composed of the above mentioned sintered apatite matrix and a reinforcing mineral fiber material which is not substantially deteriorated and not substantially bonded to the sintered apatite. The features of the present invention are exhibited if at least about 30%, generally 40% or more, and preferably about 60% or more by weight, of the sintered crystals are composed of the needle-like crystals which are entangled together, although normally the crystals consist essentially of the needle-like crystals. The present invention will be better understood by reference to the accompanying drawings in which: Fig. 1 is a scanning electrophotomicrograph (magnification x 30,000) of a sintered hydroxyapatite body according to the present invention, showing the fine needle like crystalline structures thereof, and Fig. 2 is a scanning electrophotomicrograph (magnification x 7,500) of a sintered hydroxyapatite body according to a conventional sintering process at a high temperature, showing the hexagonal-system crystalline structures thereof. The apatites used in the present invention include, hydroxyapatite, carbonate-apatite, fluoroapatite, chloroapatite, mixtures thereof, and mixtures of subunit materials thereof which are converted to these apatites in the course of the baking step hereinafter referred to as an apatite precursor). Apatite compounds are broadly defined by the following formula (I); A10 (X04)6 Zm -------- (I) wherein, A =' Ca, Pb, Mn, Na, K, etc.; X = P, As, V, Si, etc.; Z = OH, CO3, F, Cl; and m is a number to satisfy the atomic valences. The apatite to be used in the present invention, however, is more limited. The apatites used in the present invention are those compounds which have fundamental structures represented by the following formula (II) and of which the atomic ratio of calcium to phosphorus (hereinafter referred to as Ca/P ratio) is within the range specified below; Ca (PO4)6Zm --------wherein, Z is selected from OH, CO3, F, Cl and mixtures thereof, and m is a number satisfying atomic valences substantially (e.g., 2 or 1). More specifically, in the formula (II) given above, the Ca/P ratio is not necessarily a stoichiometric ratio (5/3) but can be a non-stoichiometric ratio. In general, the Ca/P ratio is approximately in the range of 4/3 to 11/6 and preferably about 9/6 to about 5/3. If required an inorganic non-phosphorus calcium compound such as calcium hydroxide can be intimately mixed with an apatite material having a Ca/P ratio of less than 5/3 to adjust its Ca/P ratio to about 5/3. In the case where a carbonate group-containing calcium compound such as calcium carbonate is used therefor, a sintered apatite body or apatite-fiber composite containing C03 groups can be obtained by baking the materials at a temperature lower than the decomposition temperature of the carbonate compound. It is to be noted that, in the apatite represented by the formula (II), the Ca and/or P atom may be substituted by a small or impure amount of other atoms as illustrated in the definition of formula (I) The symbol Z in formula (II) above can be one or two or more atoms or groups selected from OH, C03, F and Cl. In this case, the apatite is herein classified into hydroxy-apatite, carbonate-apatite, fluoroapatite or chloroapatite, respectively, in accordance with the largest amount of OH, CO3, F or Cl contained therein. All these apatites fall within the same hexagonal crystalline system, space group C63/m, and chemical formula number in unit lattice, and thus they have substantially the same sintering properties and similar physical properties. These apatites are available commercially and can be purified as necessary, or can be synthesized chemically. From the viewpoint of uses and the like, the apatite to be used in the present invention is preferably hydroxy apatite represented by the formula (II) above wherein substantially all or a major amount (normally about 90% or more) of Z is OH group and the balance amount (normally about 10% or less) of Z if any is the other substituents. For bioceramic uses, the balance of Z if any is preferred to be substantially CO3 group. By the term "a matrix amount" of apatite used with respect to the apatite-fiber material composite is meant the amount of the apatite material which can bind a reinforcing mineral fiber material (hereinafter sometimes referred to as fiber material) by the sintered apatite to form the sintered composite. The term "an effective amount" of the fiber material means the amount thereof which can reinforce the sintered composite and can be bound by the sintered apatite matrix to form the sintered composite. Although the effective amount of the fiber material depends on the density and the like of the fiber material to be used, the ratio-of the effective amount of fiber materials to the matrix amount of apatites is by weight preferably in the range of 0.5-70t to 99.5-30%, desirably 1-50% to 99-50%, preferably 2-40% to 98-60%, more preferably 5-30% to 95-70%, and typically 7-25% to 93-75%. Consequently, the actual amount of the fiber material is in the range of about 1% to about 50% by weight, and the amount of the apatite material is in the range of about 99% to about 50% by weight. The sintered composite of the present invention can, of course, also contain optional materials such as fillers and coloring agents which are compatible with the apatite and fiber materials and are inert under the conditions of baking, machining and uses, so far as the properties of the resulting composite are not substantially deteriorated. The mineral fiber materials to be used essentially as reinforcing materials encompass mineral (i.e. inorganic or metallic) fiber materials which have sufficient strength and will not be substantially deteriorated when they are baked in contact with the apatite material in the presence of moisture for at least 0.5 hour at a sintering temperature higher than about 1500C and preferably above 1700C (but lower than 10000C or 8O00C). The fiber materials preferred for use in the present invention preferably include, for example, mullite fibers (800"C), nitrogenmodified mullite (Sialon) fibers (1000"C), silicon carbide fibers (8000C), carbon fibers (500"C), apatite glass fibers (7500C), glass fibers and alkali-resistant glass fibers (5000C), as well as silicon nitride fibers (1000"C), silica fibers (10000C), alumina fibers (1000"C), and the like, the temperatures shown in the parentheses being the approximate maximum values at which the fiber-containing apatite composite material can be baked according to the present invention without deteriorating the properties of the fiber material or the sintered apatite. Moreover, chemically inert metallic fiber materials such as metallic fibers coated thereon with an inorganic element or compound or substantially inert metallic fibers can also be used as the reinforcing fiber materials. Coated metallic fibers are generally preferred. For example, boron fibers wherein boron was vapor-deposited onto tungsten fibers can be advantageously used. These reinforcing fiber materials are not restricted to the materials illustrated above and can be used alone or as optional mixtures thereof, as far as they exhibit satisfactory reinforcing effects and are not deteriorated in the course of baking. As to the forms and dimensions of the reinforcing fiber materials, technical knowledge of conventional glass fiber-synthetic resin composites can be applied. For example, they can be in the form of short fibers, long fibers, fiber yarns, fiber strands, wooly fibers, whiskers, nonwoven or woven fabrics, mixtures thereof, and the like. In the case of short fibers, the fiber length thereof is desirably longer than the crystal length of the sintered apatite. The distribution of the mineral fiber material in the present sintered apatite composite can be in a state substantially orientated mono-, bi- or triaxially or in a state substantially unorientated and distributed irregularly. Also, the distribution of the fiber material can be uniformly dispersed in the sintered apatite matrix or dispersed variably, dense (or rare or zero) toward the core of the composite and rare or zero (or dense) toward the surfaces of the composite. It is preferred that the fiber material is distributed dense toward the surface and is not exposed to the surface from the viewpoint of stress-resistant structural materials. The sintered apatite body of the present invention can be produced by baking the above mantioned apatite material under pressure in the presence of a suitable amount of water at a temperature of about 1500C to less than 10000C and preferably about 1600C to about 8000C. When the sintering temperature is lower, the needle-like crystalline structures peculiar to the present sintered apatite tend to become finer and increase in mechanical strength. This tendency is markedly noted when the sintering temperature is normally about 700.OC or less, especially about 6000C or less and typically about 5000C or less, although the sintering is accelerated at a higher temperature. Thus, the lower sintering temperature is generally preferred in the present invention from the viewpoint of the enhanced mechanical properties of the resulting sintered body or composite. Usually, the amount of water to be coexisting with the apatite material in the baking step is in addition to crystal water, an amount of non-crystal water (i.e. water except crystal water) in the range of 0.018 to about 25%, preferably about 0.05% to about 20%, more preferably about 0.1% to about 20% and typically about 3% to about 18% by weight of the apatite material used. When the amount of water is large, the sintering of the apatite tends to be accelerated. In the case where the water is more than about 25% and pressure is relatively low, the voices of the resulting sintered apatite will generally become too large. However, when the apatite is baked in an open-heating means such as a hot press, the amount of water to be charged may be larger than 25%. In the same fashion and conditions as described above, the mineral fiber-sintered apatite composite of the present invention can be produced by baking a matrix amount of the apatite material and an effective amount of the reinforcing mineral fiber material in a substantially contacted state at a temperature defined above and lower than the temperature causing substantial deterioration of the fiber material and substantial bonding thereof to the apatite material. Although the sintering mechanism of the apatite in the present invention has not yet been fully clarified, it is assumed that the apatite is dissolved and separated out at the baking temperature and then the separated apatite is recrystallized, entangled together and sintered. The dissolution and separation of apatite tend to be promoted under a higher pressure and/or in the presence of sufficient water. In this connection, in accordance with the present invention, the baking or sintering temperature can be considerably lowered under a higher pressure and in the presence of sufficient water in the baking step. Thus, the pressure to be employed in the sintering of the present invention is at least about 5 kgf/cm21 preferably about 50 kgf/cm2 or more, and typically about 500 kgf/cm2 or more. In the baking step of the present invention, conventional techniques known to the sintering art can be employed. For example, a hot press method under a steam atmosphere can be used, or a closed heating method under pressure by means of an autoclave and the like, a closed highfrequency heating method under pressure, a hot isotactic pressing method, etc. The typical methods for the baking are summarized in the following. The time of baking is generally in the range of about 0.5 to about 30 hours. (i) Hot press method The material such as an apatite material, a mixture of an apatite material and a mineral fiber material1 or a premolded article thereof may be baked at a temperature defined above by means of a hot press under a pressure of about 5 kgf/cm2 or more by applying thereto an atmosphere of steam or a steam-containing inert gas, preferably at a temperature of about 1500C to about 5000C under a pressure of about 10 to about 1000 kgf/cm2. This method, however, may be rather difficult to give constant sintering conditions. (ii) Closed heating method under pressure The material as mentioned above may be baked in the presence of water at a temperature defined above by means of a pressure-proof vessel such as an autoclave under a pressure of five to several tousands atmospheres. When both the temperature and pressure are relatively low, a relatively longer time is needed for sintering the material. When the pressure is as high as 1000 kgf/cm2 or more, the sintering can be advantageously conducted even at a temperature of 1500C to about 200 C. Preferably, the material can be baked at a temperature of about 1500C to about 5000C under a pressure of about 20 to about 2000 kgf/cm2. (iii) Sintering in a sealed pressure-deformable capsule, etc. In the closed heating method, closed high-frequency heating method, hot isotactic pressing method and the like described above, the material mentioned above can be sintered more effectively by baking the material which has been sealed in a pressure-deformable chemically-inert vessel (e.g., a capsule or a tube) together with water. The baking conditions are substantially the same as in (ii) above, and preferably at a pressure of about 40 to about 3000 kgf/cm2 and a temperature of about 1500C to about 5000C. By employing such a sealed vessel, the contents of the material and water can be maintained unchanged. Of the methods described above, method (ii) is preferred and method (iii) is most preferred. An apatite material or a mixture of an apatite material and a reinforcing fiber material can be molded into a desired shape by means of pressing or the like before the baking step; or the resulting sintered apatite body or composite can be machined into a desired shape. The sintered apatite body obtained according to the present invention comprises or consists essentially of fine dense polycrystalline structures wherein the crystals are needle-like fine crystals and are entangled together, and the sintered apatite can be provided with suitable microporosity as necessary. The sintered apatite-fiber material composite is a composite wherein the fiber material is present in the unchanged state in contact with the sintered apatite matrix having the above mentioned crystalline structures, and the sintered composite can also be provided with suitable microporosity. In accordance with the sintering conditions of the present invention, the crystals of the present sintered apatite body or matrix have fine dense polycrystalline structures wherein the crystals comprise or consist essentially of straight and/or curved needle-like fine crystals and are entangled together, whereby the mechanical strength properties of the present sintered apatite body or apatite-fiber material composite are enhanced markedly. According to the conventional process for sintering the apatite at a temperature as high as 71000C, the resulting sintered apatite is composed of relatively large hexagonal system crystals, and thus has markedly decreased mechanical strength properties. The strength properties of the sintered apatite body or composite is naturally reduced when the void volume or pore size of the sintered apatite body or matrix is too large. In order to obtain a sintered apatite body or composite having both excellent strength and sufficient microporosity, it is desired that the sintering process is carried out under a relatively high pressure at a temperature as low as possible in the presence of moisture. The micropores obtained according to the present invention are normally in the form of open (continous) pores. The properties of the sintered apatite body and the sintered apatite-fiber material composite according to the present invention can have, for example, the following approximate values. (a) Mean diameter of sintered apatite crystals: 0.01 to 5 m O (b) Mean length of sintered apatite crystals: 1 to 1000 m (c) Mean pore size of sintered apatite: 5 to 1000 m (d) Voids of sintered apatite: 0 to 60% by volume (e) Compression strength of sintered apatite: 300 to 1500 kgf(cm2 (f) Bending strength of sintered apatite: 100 to 800 kgf/cm2 (g) Impact strength of sintered apatite: 10 to 40 kgf.cm/cm2 (h) Tensile strength of sintered apatite: 40 to 70 kgf/cm2 (i) Compression strength of sintered composite: 350 to 2000 kgf/cm2 (j) Bending strength of sintered composite: 1000 to 3500 kgf/cm2 (k) Impact strength (charpy) of sintered composite: 56 to 200 kgf.cm/cm2 (l) Tensile strength of sintered composite: 70 to 350 kgf/cm2 Some typical properties of conventional sintered apatite bodies and composites, which were sintered at about 11000C by means of a hot press without a steam atmosphere applied thereto, are shown in Comparative Examples I to III below. The sintered apatite body and apatite-fiber composite can be advantageously applied in a broad range of uses and especially in fields where strength properties are required. Typical applications are ceramic materials which need strength properties, electronics materials, filter materials, chromatographic carriers, sensor elements (especially for physiological use), bioceramics (e.g. artificial bone, tooth and joint for the human or animal bodies), other uses where conventional fine ceramics are utilized, and the like. The above mentioned applications can be classified into industrial ceramic materials and bioceramic materials. The bioceramics require compatibility with living organisms such as the human or animal bodies in addition to strength properties and microporosity. This compatibility will be discussed in the following. It is known that hard tissues (bone, tooth, etc.) of mammals and especially human bodies consist essentially of densified hydroxyapatite and more specifically consist of densified hydroxyapatite containing a small amount (several %) of CO3 group. In this connection, much research has been reported on using sintered hydroxyapatite bodies for artificial bone and tooth implants. For example, refer to M. JARCO et al., J. Bioeng., 1, (1977) 79 and E.B. NERY et al., J. Periodontol, 46, (1975) 328. Especially, porous sintered hydroxyapatite having a void of several percent or more has been appreciated to be practically satisfactory for compatibility with human tissues. Conventional sintered hydroxyapatite, however, is not used in practice at present, which may be essentially due to non-uniform porosity and unsatisfactory mechanical properties such as impact strength and bending strength. On the other hand, mineral fiber materials to be used in the present invention and especially fiber materials of carbon, silicon carbide, mullite, nitrogenmodified mullite (Sialon), silica, alumina, apatite glass and silicon nitride are known to have chemically and physiologically non-irritating properties as well as excellent strength and elasticity. Moreover, it has been appreciated in the art that these fiber materials are in practice satisfactory for compatability with human tissues. These fiber materials are satisfactory for the physiological compatibility especially when they are included as the composite in the sintered hydroxyapatite matri x It is generally preferred that the surface of the present composite for bioceramic uses is substantially covered with the apatite matrix, that is, the fiber material is not substantially exposed. The preferred strength properties and open micropores having a void of 3% to about 60% and normally 5% to 50% by volume which have been required for such bioceramics are sufficiently provided by the sintered hydroxyapatite body and composite according to the present invention. Thus, artificial hard tissue materials having suitable open pores, satisfactory strength properties and compatibility with human and animal bodies can be obtained according to the present invention, wherein the above described conventional problems habe been eliminated. In other words, because it has been confirmed in the art that conventional porous sintered hydroxyapatite bodies have compatibility with human tissues as shown in the above mentioned literature, the present sintered hydroxyapatite body and composite thereof im hydroxyapatite bioceramic materials have a Ca/P ratio in the vicinity of its theoretical value 5/3, e.g., in the range of about 9/6 to about 5/3. The present invention will be further explained by way of the following examples. All the apatite materials to be used in the present invention have substantially the same chemical structures, crystalline systems, sintering properties and the like. Thus, those skilled in the art can readily produce substantially the same or similar sintered apatite bodies or composites of the present invention on the basis of the disclosure herein by using the materials and/or processes other than those shown in the Examples. In the following examples, the ratios and percentages are by weight unless otherwise specified. Example 7 Hydroxyapatite containing hydroxyl group and no other atom or group as the substituent (Ca/P ratio = 95/60) was adjusted to a water content (except crystal water) of 5%. The hydroxyapatite powder was sealed in a pressuredeformable silver tube and then baked at 5000C under a pressure of 1000 kgf/cm2 for 3 hours by means of a pressuretight vessel. The resulting sintered apatite body exhibited the following properties. Compression strength 520 kgf/cm2 Bending strength 710 kgf/cm2 Tensile strength S5kgf/cm2 Impact strength (Charpy) 16 kgf.cm/cm2 Voids (open micropores) about 24% by volume The crystals of the sintered body are shown in Fig. 1 (magnification x 30,000) wherein fine needle-like crystals are entangled together. Example 2 A mixture of 85% hydroapatite powder used in Example 1 and 15% carbon fiber having a mean length of about 9 mm (thermal decomposition process grade) was adjusted to a water content of 5%. The mixture was then sealed in a pressure-deformable silver tube and baked at 4000C for 7 hours as in Example 1. The resulting sintered apatite composite exhibited the following properties, the units of the strength properties being the same as in Example 1. Compression strength 780 Bending strength 1850 Tensile strength 200 Impact strength (Charpy) 115 It was observed in the bending test that on the rupture cross-section the carbon fibers were somewhat drawn out of the cross-section surface and ruptured. This demonstrates that some sliding actions exist between the fiber material and sintered apatite in the resulting composite. Example 3 The process of Example 2 was repeated except that 15t of mullite fiber having a mean length of about 9 mm was used instead of the carbon fiber. The resulting sintered apatite composite exhibited the following properties, the units of the strength properties being the same as in Example 1. Compression strength 690 Bending strength 1720 Tensile strength 185 Impact strength (Charpy) 110 It was again observed in the bending test that the mullite fibers were somewhat drawn out of the rupture cross-section and ruptured. Example 4 Calcium carbonate powder was incorporated into the hydroxyapatite powder (Ca/P ratio = 95/60) to make the Ca/P ratio of the resulting mixture about 99/60. The mixed powder 85% was admixed with 15% of carbon fiber having a mean length of about 9 mm (thermal decomposition process grade). The resulting mixed material was adjusted to a water content of 5%, sealed in a pressure-deformable silver tube, and baked as in Example 2. The resulting sintered apatite composite exhibited the following properties, the units being the same as in Example 1. Incidentally, it is especially preferred from the viewpoint of compatibility with human tissues that the resulting composite contains a suitable amount of CO3 group. Compression strength 820 Bending strength 1870 Tensile strength 195 Example 5 The process of Example 4 was repeated except that the carbon fiber and calcium carbonate were replaced by T5% of silicon carbide fiber having a mean length of about 9 mm and by the corresponding amount of calcium hydroxide powder to make the Ca/P about 99/60, respectively. The resulting sintered apatite composite exhibited the following properties, the units being the same as in Example 1. Compression strength 835 Bending strength 1910 Tensile strength 190 Comparative Example I Hydroxyapatite containing hydroxyl group and no other atom or group as the substituent (Ca/P ratio = 95/60) was molded into a tablet about 5 mm x about 50 mm and then adjusted to a water content of 5%. The hydroxyapatite was compressed and baked at 11000C under 200 kgf/cm2 for 2 hours by means of a hot press. The resulting sintered apatite body of the conventional type exhibited the following properties, the units being the same as in Example 1. Compression strength 320 Bending strength 310 Tensile strength 35 Impact strength (Charpy) 7 The crystals of the resulting sintered body are shownin Fig. 2 (magnification x 7,500), which are composed of hexagonal system crystalline structures. Comparative Example II A mixture of 85% hydroxyapatite powder used in Comp.Ex.I and 15% carbon fiber having a mean length of about 9 mm (thermal decomposition process grade) was molded into a tablet and then adjusted to a water content of 5%. The tablet was sintered as in Comp.Example I to show the following properties, the units being the same as in Example I. Compression strength 310 Bending strength 320 Tensile strength 40 Impact strength (Charpy) 8 Comparative Example III The process of the above Comp.Ex. II was repeated except that 15% of glass fiber having a mean length of about 9 mm was used instead of the carbon fiber. The resulting sintered apatite composite exhibited the following properties, the units being the same as in Example 1. Compression strength 305 Bending strength 310 Tensile strength 45 Impact strength 8 Indicentally, in Comparative Examples II and III, it was observed in the bending test that the carbon fibers or glass fibers were ruptured on the cross-sectional surfaces. These facts demonstrate that the fiber materials were deteriorated and also firmly bonded to the sintered apatite in the resulting composites. Also, it is to be noted that the hot press sintering steps in Comparative Examples I to III were conducted without applying a steam atmosphere thereto. This sintering step corresponds to the baking of hydroxyapatite in the absence of water, since substantially all the water present in the apatite is rapidly vaporized away from the mold of the hot press. Example 6 The process of Example 2 was repeated except that 95% of the hydroxyapatite powder and 5% of carbon fiber were used. The resulting sintered apatite composite exhibited compression strength of 660 kgf/cm2.

Claims: CLAIMS: 1. A process for sintering apatite by baking an apatite material selected from hydroxyapatite, carbonate apatite, fluoroapatite, chloroapatite, precursor materials thereof, and mixtures thereof; characterized by baking the apatite material in the presence of water in addition to the crystal water thereof under pressure at a temperature lower than 10000C to substantially sinter the apatite material. 2. A process according to Claim 1, in which a matrix amount of the apatite material is baked in contact with an effective amount of a reinforcing mineral fiber material at a temperature lower than 10000C and lower than the temperature causing substantial deterioration of the fiber material. 3. A process according to Claim 1 or 2, in which the crystals of the sintered apatite have fine dense crystalline structures wherein the crystalls contain at least 30% by weight of needle-like fine crystals and are entangled together. 4. A process according to any one of Claims 1 to 3, in which the apatite has the fundamental structure represented by the following formula and the atomic ratio of calcium to phosphorus in the apatite is in the range of 4/3 to 11/6; Ca10(PO4)6Zm wherein,Z is selected from OH, CO3, F, Cl and mixtures thereof and m is a number satisfying atomic valences. 5. A process according to any one of Claims 1 to 4, in which a small amount of an inorganic non-phosphorus calcium compound is intimately mixed with an apatite material having a calcium/phosphorus ratio of less than 5/3 to adjust the Ca/P ratio of the apatite material to about 5/3. 6. A sintered apatite composite comprising a reinforcing material and a sintered apatite matrix wherein the apatite is selected from hydroxyapatite, carbonate apatite, fluoroapatite, chloroapatite and mixtures thereof, consisting essentially of an effective amount of a reinforcing mineral fiber material and a matrix amount of sintered apatite in contact with the fiber material, the crystals of the sintered apatite having fine dense crystalline structures comprising at least about 30% by weight of needle-like fine crystals and are entangled together, and the fiber material is not substantially deteriorated. 7. A composite according to Claim 6, in which the apatite has the fundamental structure represented by the following formula and the atomic ratio of calcium to phosphorus in the apatite is in the range of 4/3 to 11/6; Ca10(PO4)6Zm wherein, Z is selected from OH, CO3, F, Cl and mixtures thereof and m is a number satisfying atomic valences. 8. A composite according to Claim 6 or 7, in which the amount of the fiber material is in the range of about 1% to about 50% by weight and the amount of the apatite material is in the range of about 99% to about 508 by weight. 9. A composite according to any one of Claims 6 to 8, in which the sintered apatite has open pore voids of 3% to 60% by volume, preferably of 5% to 50% by volume. CLAIMS: 1. A process for sintering apatite by baking an apatite material selected from hydroxyapatite, carbonate apatite, fluoroapatite, chloroapatite, precursor materials thereof, and mixtures thereof; characterized by baking the apatite material in the presence of water in addition to the crystal water thereof under pressure at a temperature lower than 10000C to substantially sinter the apatite material. 2. A process according to Claim 1, in which a matrix amount of the apatite material is baked in contact withan effective amount of a reinforcing mineral fiber material at a temperature lower than 10000C and lower than the temperature causing substantial deterioration of the fiber material. 3. A process according to Claim 1 or 2, in which the crystals of the sintered apatite have fine dense crystalline structures wherein the crystalls contain at least 30% by weight of needle-like fine crystals and are entangled together. 4. A process according to any one of Claims 1 to 3, in which the apatite has the fundamental structure represented by the following formula and the atomic ratio of calcium to phosphorus in the apatite is in the range of 4/3 to 11/6; Cal0(P04)6Zm wherein,Z is selected from OH, CO3, F, Cl and mixtures thereof and m is a number satisfying atomic valences.

Inventors: HATAHIRA, SEIICHI
Applicants: INA SEITO CO., LTD
Application year: 1983
Main classification: C04B35
IPC codes: C04B35, A61F2, A61L27