JPH0292862A - Sintered compact capable of ion elution - Google Patents

Abstract

PURPOSE:To obtain the title sintered compact capable of eluting ions to be fed for biological reactions by calcining a multiple oxide of four-component transition metal consisting of Mn, Ni, Co and Fe. CONSTITUTION:MnO2, NiO, CoO and FeO are mutually mixed so as to be ca.3:1:1:1 in the molar ratio Mn:Ni:Co:Fe, and the resultant mixture is then preliminarily calcined at 900-1100 deg.C followed by pulverization into granules <=50mu in size. The granules is then put to press forming under 8-13tons/cm<2> for several to several tens sec. followed by green sheet forming and then main calcination at 1200-1500 deg.C. The resulting product is then put to cutting process into granules, thus obtaining the objective sintered compact from multiple oxide of four-component transition metal made up of Mn, Ni, Co and Fe.

Description

[Detailed Description of the Invention] (Object and Field of the Invention) In recent years, research on biological reactions has revealed that transition metal ions such as manganese, molybdenum, iron, copper, cobalt, and zinc have strong bonding forces with biological ligands. Therefore, it has been clarified that they often play a central role in the activity of enzymes and proteins during metabolism, proliferation, etc. of living organisms.

Since these ions are said to have catalytic functions in enzyme reactions, protein synthesis reactions, etc., it is extremely important to constantly and sequentially supply these transition metal ions for the smooth execution of biological reactions. be.

An object of the present invention is to provide a sintered body that elutes at least manganese, nickel, cobalt, and copper ions among the transition metal ions, and elutes ions that can be supplied to biological reactions.

(Structure of the Invention) As described in the claims, the structure of the present invention is as follows: (1) An ion-eluting sintered body made of a composite oxide having four components: manganese, nickel, cobalt, and iron.

■An ion-eluting sintered body made of a composite oxide containing four components: copper, manganese, nickel, cobalt, and iron.

(3) Ion-eluting sintered body made of a composite oxide containing five components: manganese, nickel, cobalt, iron, and copper.

(2) The ion-eluting sintered body according to claims (1), (2), and (3) is obtained by mixing some or all of an alkali metal oxide, an alkaline earth metal oxide, and a rare earth oxide.

A typical manufacturing process for the sintered body of the present application is as shown below.

Raw material powder weighing (weighing accuracy 1/100 to 1/1000)
-Blending ratio (5 hours to 24 hours) → Calcination (900℃ to 1
100℃) - Finely pulverized C particle size 50μ or less) → Pressure molding (pressure crab 8tons/cm" ~ 13tons/errI
'', pressurization time: several seconds to several tens of seconds) → green sheet molding - main firing (120 (1 ° C. to 1500 ° C.) → cutting into granules (Example) of the sintered body described in (1) above The manufacturing process of a sintered body in which the molar ratio of manganese, nickel, cobalt, and iron is 3:1:1:1 is shown.

Mn 02 280gr, Ni 092gr, Co02
Weigh 0gr and Fe0110gr with an accuracy of 1/100,
The entire amount is put into a container containing an appropriate amount of water and 1 kg of natural agate stone, and calcined in a lab mill for about 5 hours. This fired powder is mixed and ground again in a lab mill, adjusted to fine particles with a particle size of 50μ or less, and after molding. Main firing is performed in an electric furnace at 1300°C to form a ceramic.

Firing time was 12 hours, 0℃→440℃, 400℃
→ Divided into three temperature stages: 1100°C, 1100°C → 1300°C, and held for several tens of minutes at each stage.
The main firing time at 300°C was approximately 2 hours, and the firing was performed using a program in which the temperature was raised to 1300°C for 4 hours, and the temperature was lowered for 6 hours. In addition, oxygen supplementation was not performed during the main firing.

A typical method for producing the sintered body of the present application is as shown in the above steps and examples, but the method for obtaining the sintered body of the present application is not limited to the above steps and examples. do not have.

Further, the sintered body obtained in the above example contains manganese oxide (MnO), nickel oxide (Nip), cobalt oxide (
It is not a mixture of ferrous oxide (Coo) or ferrous oxide (Fed), but a composite oxide made of these. In the case of the example, this is supported by the fact that the spectrum at the position corresponding to the metal oxide is extremely smooth.

(Operations and Effects of the Invention) Among the inventions of the present application, the sintered bodies and their fine powders obtained in the above examples were used as materials, and each material was washed with pure water, dried, and immersed in 100 cc of a physiological electrolyte solution. After 30 seconds while adjusting the temperature of the solution, a certain amount of supernatant liquid is collected, and the total concentration of eluted ions of the metal elements forming the composite oxide is detected by measuring the ionic equivalent conductivity. Furthermore, each metal ion was quantified using an atomic absorption spectrometry table.

Ion equivalent conductivity was measured using an IonMabi ion micrograph device manufactured by Dyonex, USA, and a Seikosha plasma analyzer was used for atomic absorption spectrometry. As a result, the following results were obtained.

(1) In the case of a sintered body (however, the weight of the material used is 1 g, and the surface area is approximately 1
Diameter 25.5+em, thickness 1m with O square crn'
liquid temperature ion Atomic absorption spectroscopy (mg #21 ('C)
Conductivity (ppm) Mn Fe Co Ni5
0.001 0.001 0.002 0.0027
0.002 0.002 0.003 0.0038
0.003 0.002 0.004 0.00311
0.004 0.005 0.006 0.0031
0 0.004 0.005 0.006 0.003
■For fine powder materials (however, the weight of the materials used is 32Mesh-64Mes)
1 with fine powder flow due to sieving with h sieve
) Liquid temperature Ion Atomic absorption spectroscopy (mg/β) ('C)
Conductivity (ppm) Mn Fe Co Ni15
458 0.105 0.100
0.250 0.19825 720 0.
220 0.206 0.340 0.3
0 mouth 35 785 0.315 0.206 0.4
98 0.30042 992 0.410 0.4
85 0.720 0.30050 954 0.4
08 0.490 0.715 0.300 Above table (1
) and (2), it is found that when the sintered body of the present application or its powder is immersed in an electrolyte solution, transition metal elements are ionized, and metal ions are eluted into the solution.

This has characteristics not found in conventional metal oxides.

Unlike conventional metal oxides, the sintered body of the present application is immersed in an electrolyte solution. It is thought that the bond between metal ions and oxygen ions is weaker than in simple metal oxides, and the metal ions are more likely to be liberated. Theoretical elucidation has not been sufficiently carried out.

The sintered body according to the above example was formed into a thin plate shape, and this was given to outpatients and inpatients complaining of knee joint line and shoulder stiffness at a university hospital in Tokyo and a hospital in Osaka prefecture.
When testing whether there was any effect on the knee or shoulder area for 8 weeks, it was found that the knee joint line was significantly effective in 4 out of 9 patients, and in 2 patients. There was a slight effect on 2 people, and the rest
One person did not see any effect.

On the other hand, for shoulder stiffness, one of the 12 patients had a significant effect, five had an effect, four had a slight effect, and the remaining one had no effect. Ta.

The above results reveal that the sintered body of the above example had a certain therapeutic effect on the diseased area, but
This is because the sintered powder penetrates through the skin of the diseased area and elutes transition metal ions inside the body, which applies continuous stimulation to the diseased area and causes continuous excitement to the nerves in the diseased area. It is understood that when given, an analgesic effect is produced.

In addition, when a garland chrysanthemum is planted in a body of a certain size, (1) tap water in which the sintered body according to the above example was immersed is added, ■ tap water is added, (3) distilled water only. When comparing , etc., it was found that the most remarkable growth of garland chrysanthemums was seen in the case of (+), the growth was extremely slow in the case of (3), and the case of ■ was in between. .

That is, it is thought that the sintered body of the present application also affects the physiology of plants, and when immersed in the body of a plant, transition metal ions are eluted, thereby affecting the growth of the composition of the plant.

As described above, the sintered body or powder thereof of the present invention exhibits a relatively rare phenomenon in which transition metal ions are eluted into water, which stimulates the nerves in living bodies and can be used as medicines and agricultural cultivation promotion products. Since there is an extremely large possibility that this invention will be implemented in the future, the present invention should be said to be extremely promising and useful.

Claims (4)

[Claims] (1) An ion-eluting sintered body made of a composite oxide containing four components: manganese, nickel, cobalt, and iron. (2) An ion-eluting sintered body made of a composite oxide having four components selected from copper and three of manganese, nickel, cobalt, and iron. (3) Ion-eluting sintered body made of a composite oxide containing five components: manganese, nickel, cobalt, iron, and copper. (4) Alkali metal oxide, alkaline earth metal oxide,
An ion-eluting sintered body according to claims (1), (2), and (3), which is obtained by mixing a part or all of a rare earth oxide.