CN112872353B

CN112872353B - Preparation method of self-heating porous titanium-based administration atomization core easy to assemble

Info

Publication number: CN112872353B
Application number: CN202110028221.XA
Authority: CN
Inventors: 杨芳; 常慧荣; 张耕秋; 郭志猛; 秦乾; 陈存广; 祁妙; 邵艳茹
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 2021-01-08
Filing date: 2021-01-08
Publication date: 2022-01-11
Anticipated expiration: 2041-01-08
Also published as: CN112872353A

Abstract

A preparation method of a self-heating porous titanium-based drug delivery atomizing core easy to assemble belongs to the field of porous functional materials. The invention adopts a clamping groove type structure to realize the assembly of the porous titanium-based administration atomizing core, improves the resistivity of the porous titanium-based administration atomizing core by adding alloy elements to realize the self-heating of the administration atomizing core, and prepares the self-heating porous titanium-based administration atomizing core by the technologies of injection molding, compression molding, gel injection molding and the like. Aiming at the problem that the traditional atomization core is difficult to assemble, the invention provides the method for realizing the assembly of the porous titanium-based drug delivery atomization core by adopting a clamping groove type structure, so that the use of the traditional heating resistance layer material is saved, and the problems of oxidation, brittleness and the like of a resistance wire in the high-temperature sintering process are avoided; in order to realize self-heating of the dosing atomization core, the resistivity of the porous titanium-based dosing atomization core is improved by adding alloy elements, the functions of medicine storage and medicine oil heating are integrated, the installation is convenient, the manual assembly cost is greatly reduced, the automatic production line is convenient to realize, and the self-heating dosing atomization core has the advantage of high applicability.

Description

Preparation method of self-heating porous titanium-based administration atomization core easy to assemble

Technical Field

The invention belongs to the field of porous functional materials, and provides a preparation method for preparing a self-heating porous titanium-based administration atomizing core which is easy to assemble by various forming modes such as compression molding, injection molding, gel casting and the like.

Background

Titanium not only has higher specific strength and better oxidation resistance and corrosion resistance, but also has the advantages of safety, no toxicity, controllable pores and the like, so that the titanium is often used for medical framework materials, filter core materials and the like. Therefore, the porous titanium-based material is used as the atomizing core matrix, and the medicine is conducted and atomized by the power of an external power supply, so that the atomizing core matrix has the characteristics of safety, no toxicity, oxidation resistance, corrosion resistance, good chemical stability and the like. However, the porous titanium-based atomizing core has not achieved self-heating due to the low resistivity of titanium.

At present, the porous titanium-based administration atomization core mostly realizes the heating administration of the atomization core by utilizing heating resistance layer materials such as nickel chromium, nickel chromium iron and the like. Generally speaking, the heating resistance layer is fixed with the atomizing core in a combined manner through welding, printing, integrated sintering and the like, and then is connected with the positive electrode and the negative electrode in a welding manner, so that the heating resistance layer generates heat in the use process, and the atomizing core achieves the purpose of administration atomization. However, because the melting point of titanium is high and the sintering temperature of the porous titanium blank is high, the heating resistor layer material is embrittled due to excessive growth of crystal grains in the integrated sintering process, and is very easy to break in the assembling process, so that heating cannot be performed; in addition, the contact between the heating resistor layer and the positive and negative electrodes by welding, printing and the like involves a large amount of human resources, has low production efficiency and is not beneficial to realizing industrialized mass production. Therefore, how to realize simple assembly and self-heating of the porous titanium-based drug delivery atomizing core is one of the key points of the development of the porous titanium-based drug delivery atomizing core at present.

Disclosure of Invention

The invention provides a preparation method of a self-heating porous titanium-based administration atomizing core easy to assemble, which adopts a clamping groove type structure to realize the assembly of the porous titanium-based administration atomizing core, saves the use of the traditional heating resistance layer material, saves the complex process for preparing the atomizing core and a heating component on one hand, can avoid the problems of embrittlement, fracture and the like of the heating component caused by excessively long crystal grains in the high-temperature sintering process, realizes the self-heating administration of the atomizing core, and on the other hand, ensures that an atomizer becomes small and portable, and can customize the atomizing core meeting the specification according to the requirements of different body administration parts on the particle size of the atomized medicine. Meanwhile, in order to realize self-heating of the administration atomization core, the resistivity of the porous titanium-based administration atomization core is improved by adding alloy elements, so that the problem of low resistivity of the titanium alloy is solved; the porous titanium-based drug delivery atomizing core is prepared by the technologies of compression molding, injection molding, gel injection molding and the like, the shape and the size of the atomizing core can be customized, and the design is more free and flexible. The personalized customization of atomizing core of dosing can be realized, existing simple process, reduce cost's advantage, and the draw-in groove formula assembly design is easy to assemble simultaneously, reduces the manual assembly cost by a wide margin, is convenient for realize automatic production line, has the advantage that the suitability is high.

In order to obtain the self-heating porous titanium-based administration atomizing core easy to assemble, the preparation method is characterized by comprising the following steps:

(1) mixing raw materials: weighing titanium raw material powder, alloy powder and a pore-forming agent according to a certain proportion, mixing in a mixer for 2-6 h, and uniformly mixing to obtain mixed powder.

(2) Preparing a forming material: and (2) mixing the mixed powder in the step (1) and a binder or a solvent in proportion according to the molding requirement, and mixing materials in a ball milling mode for 0.5-2 hours to obtain a uniform molding material.

(3) Forming a blank body: forming the forming material in the step (2) according to a target shape to obtain an atomized core blank; the blank forming mode comprises compression molding, injection molding or gel injection molding.

(4) Degreasing and sintering: degreasing the atomized core blank in the step (3) at 250-650 ℃, and keeping the temperature for 0.5-5 h; and then, sintering in a vacuum sintering furnace in vacuum or argon, wherein the sintering temperature is 1000-1300 ℃, preserving the heat for 60-200 min, and cooling to obtain the self-heating porous titanium-based administration atomization core.

Further, the titanium raw material powder in the step (1) is titanium powder or titanium alloy powder; the alloy powder is one or more of aluminum powder, copper powder or iron powder; the pore-forming agent is paraffin, sodium chloride, potassium chloride and the like. Wherein the alloy powder accounts for 10-40 wt% of the total amount, the pore-forming agent accounts for 5-30 wt% of the total amount, and the balance is titanium raw material powder.

Further, the binder in the step (2) is one or more of ethylene-vinyl acetate copolymer (EVA), Paraffin (PW), Polyethylene (PE), polypropylene (PP), Polyformaldehyde (POM), Stearic Acid (SA), and the like; the solvent is one or more of deionized water, acetone, ethanol, xylene or toluene and the like; the solid content of the forming material is 55-95 vol.%, and the balance is an adhesive or a solvent.

Further, the blank forming mode in the step (3) is press forming, and the specific steps are as follows:

1) granulating the forming material in the step (2), and then screening the forming material through a 60-100-mesh screen to obtain a sample pressing material;

2) lubricating oil or zinc stearate is smeared on the surface of the die, so that the die is convenient to demould;

3) and (3) carrying out compression molding on the sample pressing material, wherein the molding pressure is 10-50 MPa, and the pressure maintaining time is 3-10 s.

Further, the blank molding manner in the step (3) is injection molding, and the specific steps in the step (3) are as follows:

1) mixing the forming material in the step (2) to obtain a mixture;

2) putting the mixture into a crushing granulator for crushing and granulating to obtain a feed for injection;

3) injecting the injection feed at 160-200 ℃ and under the pressure of 10-50 MPa for injection molding, maintaining the pressure for 5-10 s, and then demolding to obtain a blank;

4) and carrying out acid stripping or dissolution stripping treatment on the injection blank to obtain an atomization core blank with a target shape.

Further, the blank forming mode in the step (3) is gel casting, and the specific steps in the step (3) are as follows:

1) adding 0.02-0.1wt.% of oleic acid and 0.05-0.2wt.% of PVB solution into the forming material in the step (2), and uniformly mixing to obtain mixed slurry;

2) pouring the mixed slurry into a silica gel sheath, and drying at 25-40 ℃ for 4-10 h;

3) and taking the dried green body out of the sheath to obtain the atomized core green body with the target shape.

Further, the self-heating porous titanium-based administration atomization core in the step (4) is fixed through the metal clamping groove, so that the core is in contact with the positive electrode and the negative electrode, and administration atomization effect is generated through self-heating.

The key points of the technology of the invention are as follows: (1) 10-40 wt.% of alloy powder such as Al, Fe, Cu and the like is added into the titanium matrix, and the resistivity of the titanium-based atomizing core is regulated, so that the self-heating of the atomizing core is realized, and the use of a traditional heating wire is omitted. The alloy content is controlled to be 10-40 wt.% and is obtained by verifying and controlling the atomization core resistance to cooperate with the drug administration atomization effect through a large number of experiments. (2) The porous titanium-based administration atomization core is fixed through the metal clamping groove, so that the atomization core is in contact with a positive electrode and a negative electrode of an atomizer, self-heating of the titanium-based atomization core is realized through electrode electrification, heating through a heating wire is not needed, and contact between the electrode and the heating wire through welding, printing and other modes is also omitted.

The invention has the advantages that:

1. the titanium and the titanium alloy have stable chemical properties, do not generate chemical pollution to liquid medicine, have good biocompatibility, and are safe and nontoxic in raw materials and friendly to human bodies.

2. Alloy elements such as Al, Fe, Cu and the like are added into the titanium matrix, so that the resistivity of the material is greatly improved, the titanium matrix atomizing core can realize self-heating, the contact area with medicinal oil is large, and the atomizing effect is greatly improved.

3. The use of the traditional heating resistance layer material is omitted, the problems of embrittlement, fracture and the like of the heating component caused by excessively grown crystal grains in the high-temperature sintering process can be avoided, the complex process for preparing the atomizing core and the heating component is omitted, and the administration effect is realized through the self-heating of the atomizing core.

4. The porosity is controllable, and is small and exquisite light, can realize the customization of the shape size of atomizing core, and the design is more flexible and free.

5. The forming method is various, the near-net forming can be realized, the material utilization rate is improved, and the processing cost is reduced.

6. The clamping groove type structure realizes the assembly of the porous titanium-based dosing atomization core, is convenient to install, greatly reduces the manual assembly cost, is convenient to realize an automatic production line, and has the advantage of high applicability.

Description of the drawings:

FIG. 1 is a schematic front view showing the structure of a self-heating titanium-based porous atomizing core which is easy to assemble and is prepared according to an embodiment of the present invention.

FIG. 2 is a schematic top view of an easily assembled self-heating titanium-based porous atomizing core prepared in accordance with an embodiment of the present invention.

Detailed Description

Example 1:

the self-heating porous titanium-based administration atomization core easy to assemble is prepared by the following steps:

(1) weighing the titanium powder, 30wt.% of iron powder and 20 wt.% of potassium chloride according to a ratio, then putting the materials into a mixer for mixing for 2 hours, and uniformly mixing to obtain mixed powder.

(2) And mixing the mixed powder with 5vol.% of paraffin, performing ball milling and mixing for 0.5h, then granulating, and screening by using a 100-mesh screen to obtain the sample pressing material.

(3) And (3) coating lubricating oil or zinc stearate on the surface of the die, filling the sample pressing material into a pressing die with a target shape, performing compression molding under the pressure of 50MPa, maintaining the pressure for 10s, and taking out to obtain a blank with a required shape.

(4) And (3) placing the blank in a sintering furnace, sintering by argon, preserving heat for 4h at 400 ℃, preserving heat for 90min at 1200 ℃, and cooling to obtain the required self-heating porous titanium-based administration atomization core.

Example 2:

(1) weighing titanium alloy powder and aluminum powder according to a certain weight ratio of 4:1, adding 20 wt.% of sodium chloride, then putting into a mixer for mixing for 6 hours, and uniformly mixing to obtain mixed powder;

(2) mixing the mixed powder and a plastic-based binder for injection according to a certain proportion, wherein the mixed powder accounts for 60 vol.%, the binder accounts for 40 vol.%, mixing for 0.5h in a ball milling manner, and then mixing in an internal mixer at the mixing temperature of 180 ℃ for 60 min;

(3) putting the mixture into a crushing granulator for crushing and granulating to obtain a feed for injection;

(4) firstly, installing a mold with a target shape in place, performing injection molding on the feed for injection at 180 ℃ under the pressure of 50MPa, maintaining the pressure for 5s, and demolding to obtain a blank;

(5) carrying out acid stripping treatment on the injection blank to obtain an atomization core blank with a target shape;

(6) and (3) placing the degreased blank in a vacuum sintering furnace, respectively preserving heat for 3h at 400 ℃ and 600 ℃, preserving heat for 120min at 1200 ℃, and cooling to obtain the required self-heating porous titanium-based administration atomization core.

Example 3:

(1) weighing titanium powder, copper powder and aluminum powder according to a certain proportion, wherein the titanium powder: copper powder: aluminum powder 5: 1:2, adding 10 wt.% of paraffin, mixing for 3 hours by using a mixer, and uniformly mixing to obtain mixed powder;

(2) mixing the mixed powder and a toluene solvent according to a certain proportion, wherein the mixed powder accounts for 70 vol%, the binder accounts for 30 wt%, then adding 0.5 wt% of oleic acid and 0.2 wt% of PVB solution, and mixing for 1h to obtain mixed slurry;

(3) pouring the mixed slurry into a silica gel sheath with a target shape, drying at 40 ℃ for 4h, and waiting for solidification and forming;

(4) taking out the dried green body from the sheath to obtain an atomized core green body;

(5) and (3) placing the atomization core blank in a sintering furnace, preserving heat for 1h at 600 ℃, then sintering in vacuum at 1150 ℃, preserving heat for 200min, and cooling to obtain the required self-heating porous titanium-based administration atomization core.

Claims

1. The preparation method of the self-heating porous titanium-based administration atomization core easy to assemble is characterized by comprising the following preparation steps:

(1) mixing raw materials: weighing titanium raw material powder, alloy powder and a pore-forming agent according to a certain proportion, mixing in a mixer for 2-6 h, and uniformly mixing to obtain mixed powder;

(2) preparing a forming material: mixing the mixed powder in the step (1) and a binder or a solvent according to a forming requirement in proportion, and mixing materials in a ball milling mode for 0.5-2 hours to obtain a uniform forming material; the solid content of the forming material is 55-95 vol.%, and the balance is an adhesive or a solvent;

(3) forming a blank body: forming the forming material in the step (2) according to a target shape to obtain an atomized core blank; the blank forming mode is divided into compression molding, injection molding or gel casting;

(4) degreasing and sintering: degreasing the atomized core blank in the step (3) at 250-650 ℃, and keeping the temperature for 0.5-5 h; then, carrying out vacuum or argon sintering in a vacuum sintering furnace, wherein the sintering temperature is 1000-1300 ℃, preserving the heat for 60-200 min, and cooling to obtain the self-heating porous titanium-based drug delivery atomization core;

the titanium raw material powder in the step (1) is titanium powder or titanium alloy powder; the alloy powder is one or more of aluminum powder, copper powder or iron powder; the pore-forming agent is paraffin, sodium chloride and potassium chloride; wherein the alloy powder accounts for 10-40 wt% of the total amount, the pore-forming agent accounts for 5-30 wt% of the total amount, and the balance is titanium raw material powder;

the self-heating porous titanium-based administration atomization core in the step (4) is fixed through the metal clamping groove, so that the self-heating porous titanium-based administration atomization core is in contact with the positive electrode and the negative electrode, and administration atomization effect is generated through self-heating.

2. The method for preparing the self-heating porous titanium-based drug delivery atomizing core easy to assemble according to claim 1, is characterized in that: the binder in the step (2) is one or more of ethylene-vinyl acetate copolymer (EVA), Paraffin (PW), Polyethylene (PE), polypropylene (PP), Polyformaldehyde (POM) and Stearic Acid (SA); the solvent is one or more of deionized water, acetone, ethanol, xylene or toluene.

3. The method for preparing the self-heating porous titanium-based drug delivery atomizing core easy to assemble according to claim 1, is characterized in that: the blank forming mode in the step (3) is press forming, and the concrete forming steps are as follows:

4. The method for preparing the self-heating porous titanium-based drug delivery atomizing core easy to assemble according to claim 1, is characterized in that: the blank forming mode in the step (3) is injection forming, and the specific forming steps are as follows:

1) mixing the forming material in the step (2) to obtain a mixture;

5. The method for preparing the self-heating porous titanium-based drug delivery atomizing core easy to assemble according to claim 1, is characterized in that: the blank forming mode in the step (3) is gel casting, and the concrete forming steps are as follows: