Abstract:
A composite oxide synthesized by a citrating process and utilized in functional ceramics materials is prepared by the following process. Co-precipitants or mixtures of at least one component selected from the group consisting of carbonates, basic copper and/or hydroxides of elements which compose a composite oxide are reacted with citric acid in an aqueous solution or in an organic solvent. The elements are selected from at least one element of the group consisting of Y, rare earth elements, transition elements, and alkali metal or alkaline earth metal elements. The citrate compound formed is baked to complete the composite oxide. 
     The composite oxide synthesized by this invention has superconduction at the most temperature of 93° K. with excellent Meissner effect.

Description:
This application is a continuation of application Ser. No. 07/403,358, filed Sep. 6, 1989 abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Technical Field 
     This invention relates to a method for the synthesis of composite oxides by an improved citrating process. 
     2. Background Art 
     Generally, citrate forming processes are applied in forming particles of functional ceramic materials utilized in such as magnetic substances, catalysts, sensors, superconductors, dielectric substances and optical materials. 
     C. Marcilly et al. in the Journal of the American Ceramic Soc., 53, 56 (1970) discloses a method for synthesizing a composite oxide by mixing citric acid with nitrates and/or acetates of metals. Recently, Hirabayasi et al. in the Journal of Japan Inst., metals, 26, 10 (1987) discloses a method for synthesizing a composite oxide having superconductivity at high temperatures by mixing nitrates of Y, Ba and/or Cu with citric acid and ethylene glycol. 
     However, these methods for forming citrates are methods whereby citric acid is merely added to an aqueous solution of nitrates and/or acetates. Furthermore, as added citrates are merely dissolved, metallic nitrates and/or metallic acetates and citrates coexist in the solution. In this stage, citrates are not formed. Citrates are obtained after heating and condensing this solution and dehydrating. However, this procedure causes great amounts of poisonous gases such as nitric acid (HNO 3 ), nitrogen oxide (NO x ), acetic acid (CH 3  COOH) to be found. 
     Furthermore, after dehydration, gelated citrate adheres strongly and viscidly to its container, this causes difficulty in treating and decreases the overall yield. 
     Moreover, when baking citrate, it forms an oily compound and burns fiercely with much black smoke, which is very dangerous. This caramel-like compound bulges out at high temperatures and causes difficulty in finishing the baking. 
     Thus, the above mentioned prior art has many problems in both the pollution and system aspects when applied industrially. 
     It is therefore an object of this invention to provide a method for synthesizing a composite oxide which produces no poisonous gases during the procedure. 
     It is another object of this invention to provide a method for synthesizing a composite oxide which can obtain high yields. 
     It is further object of this invention to provide a method for synthesizing a composite oxide having homogeneity and high quality. 
     It is additional object of this invention to provide a method for synthesizing a composite oxide which can be established for mass productive industrialization. 
     SUMMARY OF THE INVENTION 
     This invention relates to a method for synthesizing composite oxides, utilized for ceramic materials, by a citrating process which produces no poisonous gases during the procedure. 
     Co-precipitants or a mixture of carbonates, basic-carbonates and/or hydroxides of elements which compose a composite oxide are reacted with citric acid in an aqueous solution or organic solvent. The elements are selected from at least one element of the group consisting of Y, rare earth elements, transition elements, and alkali metal or alkaline earth metal elements. The formed citrate compound is baked to complete the composite oxide. 
     According to this invention, micro particles of composite citrate can be obtained in a slurry before dehydration which have no contamination. When dehydrated, it consists only of micro particles of composite citrate and water. Therefore, no poisonous gases are produced during citrate baking. 
     Synthesized citrate shows high homogeneity when analyzed by EPMA and/or X-ray diffraction methods. According to further baking, it shows superconduction at a transition temperature of 93° K. and gives the Meissner effect to a high degree. 
     This method for synthesizing composite oxides using carbonates and/or hydroxides has excellent industrial utility compared with the prior method using nitrates and/or acetates. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     The present invention will be understood more clearly from the preferred embodiments described herebelow and from the appended drawings which illustrate the detailed composition of the embodiments, which, however, should not be taken to limit the invention but are for explanation and understanding only. 
     In the drawings: 
     FIG. 1 is a graph showing a relationship between the temperature (°K.) and resistance rate of composite oxides of EXAMPLE 1 to 4 and CONTROL 1 to 3 respectively designated 1 to 4 and 5 to 7 in the figures. 
     FIG. 2 is a graph showing a relationship between the temperature (°K.) and magnetic sensitivity of composite oxides of EXAMPLE 1 to 4 and CONTROL 1 to 3, 
     FIG. 3-1 to FIG. 9-1 are charts showing the EPMA analysis results of composite oxides including Ba and Y in EXAMPLEs 1 to 4 and CONTROLs 1 to 3, 
     FIG. 3-2 to FIG. 9-2 are charts showing the EPMA analysis results of composite oxides including Cu and Y in EXAMPLEs 1 to 4 and CONTROLs 1 to 3, 
     FIGS. 10 to 16 are charts showing X-ray diffraction pattern of composite oxides of EXAMPLEs 1 to 4 and CONTROLs 1 to 3. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In this invention, La, Nd and/or Gd may be used as the rare earth elements, Cu, Ni and/or Co as the transition metal elements, K and/or Na as the alkali metal elements and Ba, Sr and/or Ca as the alkaline earth metal elements. 
     Synthesizing temperatures composite citrates are preferable in a range of 40° to 120° C., more specifically at 65°±5° C. Additionally, temperatures for dehydrating are preferable in a range of 50° to 120° C., more specifically at 90°±5° C. Furthermore, suitable conditions for pre-baking are at temperatures of 800° to 900° C. for at least 4 hours and suitable baking conditions are at temperatures of 940° to 960° C. for at least 2 hours. Then the composite citrate will show superconductivity at 93° K. 
     The invention will be understood more concretely by the following examples of superconductor formation. 
     EXAMPLE 1 
     30.28 g of yttrium carbonate (55.88 wt % as Y 2  O 3 ), 59.17 g of barium carbonate (77.68 wt % as BaO) and 50.42 g of basic copper carbonate (70.95 wt % as CuO) were milled and mixed in an atomizing mill (Tokyo Atomizer TASM-1). 86.4 g of citric acid and 600 g of purified water were added to 100.0 g of mixture prepared previously. The reaction was performed at 65°±5° C. 
     After termination of the reaction, the slurry obtained was dehydrated at 90° C. 130.8 g of composite citrate was obtained. Pre-baking was performed at 850° C. for 6 hours, then the slurry was annealed in an electric furnace. The amount of pre-baked compound was 71 g. This can be milled in an agate mortar or a ball mill. 0.4 to 0.8 g of milled compound was pressurized at 100 to 200 kg/cm 2 , compacted into 10 mm of diameter and 1 to 2 mm thick. The compacted compound was baked again at 950° C. for 9 hours, then pellets of composite oxide were obtained. 
     EXAMPLE 2 
     30.28 g of yttrium carbonate (55.88 wt % as Y 2  O 3 ), 59.17 g of barium carbonate (77.68 wt % as BaO) and basic-copper carbonate (70.95 wt % as CuO) were milled and mixed in a ball mill (volume:900 ml, alumina) for 2 to 3 hours. 86.4 g of citric acid and 250 g of purified water were added to 100.0 g of the prepared mixture. Reaction was performed at a temperature of 90° C. 
     Then using the procedure as disclosed in EXAMPLE 1, pellets of composite oxide were obtained. 
     EXAMPLE 3 
     Y 2  O 3  was dissolved in nitric acid then 1.771 M/l of a solution of Y(NO 3 ) 3  was prepared. 84.60 ml (0.15 mol) of this solution, 78.34 g (0.30 mol) of Ba(NO 3 ) 2  and 108.6 g (0.45 mol) of Cu(NO 3 ) 2  3H 2  O were dissolved in water. Then 625 ml of 20 wt % of K 2  CO 3  (125 g, 0.90 mol as K 2  CO 3 ) was added little by little to co-precipitate carbonate of Y, Ba and Cu. Thus 140.2 g of co-precipitants were obtained by dehydrating at 80° C. for 16 hours after rinsing with water. 
     100.0 g of this co-precipitant, 84.7 g of citric acid and 600 g of purified water were mixed and reacted at a temperature of 65°±5° C. 
     After the reaction was terminated, obtained slurry was dehydrated at 90° C. and thus 127.9 g of composite citrate was obtained. 
     Then using the procedure as disclosed in EXAMPLE 1, the pellets of composite oxide were completed (however, the amount of pre-baked compound became 69.1  g). 
     EXAMPLE 4 
     21.39 g of Y(OH) 3  (79.09 wt % as Y 2  O 3 ), 44.98 g of Cu(OH) 2  (79.51 wt % as CuO) and 59.17 g of barium carbonate (77.68 wt % as BaO) were milled and mixed in an atomizing mill. 96.3 g of citric acid and 800 g of purified water were added to 100.0 g of the prepared mixture. The reaction was performed at a temperature of 90°±5° C. Then the obtained slurry was dehydrated and 145.7 g of composite citrate was obtained. 
     Then using the procedure as disclosed in EXAMPLE 1, the pellets of composite oxide were completed (however, the amount of the pre-baked compound became 79.0 g). 
     CONTROL 1 (designated by 5 in FIGS. 1 and 2). 
     16.92 ml of 1.771 M/l of Y(NO 3 ) 3  solution (0.030 mol) was prepared as in EXAMPLE 3, 15.66 g of Ba(NO 3 ) 2  (0.060 mol) and 21.40 g of Cu(NO 3 ) 2  3H 2  O (0.090 mol) were dissolved in 200 g of purified water. 17.28 g of citric acid (0.082 mol) was added to this solution and stirred substantially. 
     Then the obtained solution was condensed by dehydration with substantial stirring on a hot plate. During this stage, about 18 g (0.39 mol) of NO x  was produced as a form of NO 2 . H 2  O was also produced. The obtained citrate was gelated. Further dehydration caused the citrate to form a caramel-like compound, which adhered to an interior wall of a reactor. The adhered citrate was scraped off and milled. It was pre-baked at 850° C. for 9 hours then annealed. The amount of pre-baking compound was about 13.2 g (the amount lost was caused by adhesion to the reactor). 
     Then using the procedure as disclosed in EXAMPLE 1, the pellets of composite oxide were completed. 
     CONTROL 2 (designated by 6 in FIGS. 1 and 2). 
     17.14 g of yttrium oxide (98.7 wt % as Y 2  O 3 ), 59.17 g of barium carbonate (77.68 wt % as BaO) and 50.42 g of basic-copper carbonate (70.96 wt % as CuO) were milled and mixed in a ball mill for 3 hours. The obtained mixture was pre-baked at 850° C. for 9 hours then annealed. 
     Then using the procedure as disclosed in EXAMPLE 1, the pellets of composite oxide were completed (however, the amount of pre-baked compound became 72 g). 
     CONTROL 3 (designated by 7 in FIGS. 1 and 2). 
     The baked pellets which were obtained in control 2 were milled in an agate mortar, then pressurized again at 950° C. for 12 hours. 
     The transition temperature (Tc) and the rate of magnetization were examined in above mentioned composite oxide pellets of EXAMPLEs 1 to 4 and CONTROLs 1 to 3. The results are shown in the following Table 1., and FIGS. 1 and 2 of the drawings. FIG. 1 shows the results of measuring Tc (the relationship between the temperature (°K.) and rate of resistance), FIG. 2 shows the results of measuring the Meissner effect (the relationship between the temperature and rate of magnetic sensitivity). In these drawings, Nos. 1 to 7 correspond to each of the composite oxides which are indicated in Table 1. 
     
                       TABLE 1______________________________________            Tc      Rate of magnetic sensitivitySample   No.     (°K.)                    (× 1/4πemu/cm.sup.3)______________________________________EXAMPLE 1    1       93      -0.83EXAMPLE 2    2       91      -0.80EXAMPLE 3    3       90      -0.75EXAMPLE 4    4       92      -0.82CONTROL 1    5       91      -0.74CONTROL 2    6       &lt;77     0CONTROL 3    7       84      -0.40______________________________________ 
    
     Subsequently, EPMA analysis was applied for the composite oxides of EXAMPLEs 1 to 4 and CONTROLs 1 to 3 (Nos. 1 to 7 in the Table 1). 
     The analytic results of composite oxides including Ba and Y are shown in FIGS. 3-1, 4-1, 5-1, 6-1, 7-1, 8-1 and 9-1. The analytic results of composite oxides including Cu and Y are also shown in FIGS. 3-2, 4-2, 5-2, 6-2, 7-2, 8-2 and 9-2. Additionally, the analytic results by X-ray diffraction of the composite oxides are shown in FIGS. 10 to 16.