CN113521384B - Titanium-based material and preparation method and application thereof - Google Patents
Titanium-based material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113521384B CN113521384B CN202110760985.8A CN202110760985A CN113521384B CN 113521384 B CN113521384 B CN 113521384B CN 202110760985 A CN202110760985 A CN 202110760985A CN 113521384 B CN113521384 B CN 113521384B
- Authority
- CN
- China
- Prior art keywords
- titanium
- based material
- heat treatment
- raw material
- etching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
Abstract
The invention discloses a titanium-based material, a preparation method and application thereof. A preparation method of a titanium-based material comprises the following steps: s1, carrying out multi-step heat treatment on a titanium-based raw material; s2, carrying out acid etching on the titanium-based raw material obtained in the step S1; the etching solution adopted by the acid etching contains acid and ferrous ions. According to the preparation method of the titanium-based material, the titanium-based material with uniform appearance and a honeycomb-shaped pore structure can be obtained by adjusting the processes of the steps, so that the requirement of the implant on the raw material is better met.
Description
Technical Field
The invention belongs to the technical field of titanium-based material preparation, and particularly relates to a preparation method and application of a titanium-based material.
Background
Titanium-based materials, including titanium and titanium alloys, have excellent biocompatibility and excellent mechanical properties, and thus are increasingly widely used in the field of organ defect repair, especially in the field of oral implants, and have become the current preferred materials. However, titanium and titanium alloy as inert metal lack the ability to stimulate osteoblast and promote proliferation of osteocyte, i.e. the existing titanium-based oral implant mainly relies on the mechanical locking with alveolar bone to provide retention force, but has no bioactivity.
In order to solve the problems, the surface modification of the titanium implant becomes a hot research spot at home and abroad. In the surface modification method, a layer of film or coating with biological activity is formed on the surface of a titanium-based material to become a hot spot in the hot spot, and the common coating materials comprise hydrogel, gelatin, hydroxyapatite and other degradable materials; meanwhile, bioactive factors such as bone morphogenetic protein, bone growth promoting factors and the like can be added into the coating, so that a composite coating with bioactivity is formed; in addition, before forming above-mentioned composite coating, can also form porous structure on the titanium surface to increase frictional force, make composite coating adhere to on the titanium substrate surface better, guarantee composite coating's adhesion fastness in the use, along with the coating slowly degrades, bioactive factor releases gradually, reaches biochemical combination, the effect of the formation of induced bone tissue, consequently can reach better treatment.
However, the existing surface treatment technology is complicated and unstable, and cannot obtain a stable and uniform porous honeycomb shape on a titanium substrate, that is, the etching shape of the titanium substrate presents irregular diversity, and the requirement of the oral implant on raw materials is difficult to meet.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a titanium-based material, the surface of which has a honeycomb-shaped pore structure, the surface crystal grain size is moderate, the pore structure is uniform, and the requirements of the oral implant on the raw materials are further met.
The invention also provides a preparation method of the titanium-based material.
The invention also provides an implant prepared from the titanium-based material.
According to one aspect of the present invention, there is provided a titanium-based material; the surface of the titanium-based material is provided with a honeycomb-shaped pore structure; the aperture of the honeycomb-shaped pore structure is 0.1-5 mu m, and crystal grains with the grain diameter of 10-100 mu m are distributed in the titanium-based material.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
because the surface of the titanium-based material provided by the invention has the honeycomb-shaped pore structure, the pore diameter of the honeycomb-shaped pore structure is uniform, and the surface crystal grain size is moderate, the regeneration of bone cells can be effectively stimulated after the titanium-based material is used for preparing the oral implant, if the surface of the titanium-based material is attached with the active coating, the adhesive force between the active coating and the titanium-based material can be improved, and meanwhile, the degradation speed of the active coating can be controlled, so that a better treatment effect can be achieved.
In some embodiments of the invention, the crystal grains with the grain size of 10-100 μm are distributed on the surface of the titanium-based material in the area where the honeycomb-shaped pore structure is located.
In some embodiments of the present invention, the titanium-based material is enriched with Fe element at grain boundaries.
According to one aspect of the invention, a method for preparing a titanium-based material is provided, which comprises the following steps:
s1, carrying out two-step heat treatment on a titanium-based raw material;
s2, carrying out acid etching on the titanium-based raw material obtained in the step S1 by using an etching solution; the etching solution contains acid and ferrous ions.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) in step S1 of the invention, a multi-step heat treatment system can make the titanium-based raw material obtain equiaxial grain structure with uniform size; thereby improving the mechanical property of the obtained titanium-based material.
(2) In step S1 of the present invention, the impurities in the titanium-based raw material can be fully diffused to the grain boundary by the multi-step heat treatment system, and the concentration of the impurities in the grain boundary makes the etching reaction have preferential selectivity, i.e. the grain boundary is more easily corroded than the inside of the grain, thereby being more beneficial to obtaining the honeycomb-shaped pore structure required by the present scheme.
(3) One-step heat treatment, if the temperature and the time are slightly deviated, the appearance and the mechanical property of the obtained titanium-based material can be obviously influenced; the invention adopts multi-step heat treatment, and even if the parameters of the first heat treatment are slightly deviated, the correction can be carried out through the subsequent heat treatment, so that the obtained titanium-based material has more excellent mechanical properties and surface appearance.
(4) At present, the research on the surface treatment of the implant mainly focuses on the research on the components of etching liquid (acid etching), and neglects the regulation and control of the titanium-based material, but because the corrosion potential of the surface of the titanium-based material is higher, the corrosion potential of the titanium-based material is further improved by an oxide film on the surface of the titanium, and the impurities in the titanium-based material are concentrated at the grain boundary by the multi-step heat treatment of the step S1, in the acid etching treatment of the step S2, the impurities and other parts of the titanium-based material form a microcell locally, and form micro-couple local corrosion in the etching liquid, so the corrosion rate at the grain boundary is faster, and the formation of a honeycomb-shaped pore structure is more facilitated.
(5) Ferrous ions in the etching solution can be gradually enriched to the crystal boundary along with the progress of the etching reaction, the reaction rate of acid etching the titanium-based raw material is further accelerated, and hydrogen is continuously generated in the solution to enable the etching reaction to be stably, continuously and effectively carried out, so that the honeycomb-shaped pore structure in the scheme is obtained.
In some embodiments of the present invention, in step S1, the titanium-based raw material comprises, by mass:
Fe 0.02-0.05％；
C 0.01-0.03％；
O 0.03-0.10％；
the balance being Ti.
In some preferred embodiments of the present invention, in step S1, the titanium-based raw material further includes N, H, Al and other impurity elements.
In some preferred embodiments of the present invention, the content of N is 0.005% or less in percentage by mass of the titanium-based raw material.
In some preferred embodiments of the present invention, the content of H is 0.005% or less in mass percentage based on the titanium-based raw material.
In some preferred embodiments of the present invention, the Al content is less than or equal to 0.02% by mass of the titanium-based raw material.
In some preferred embodiments of the invention, the content of the single impurity element is less than or equal to 0.04 percent by mass of the titanium-based raw material.
In some preferred embodiments of the present invention, the total content of the impurity elements is 0.2% by mass or less.
In the invention, the impurity content in the obtained titanium-based material (product) is controlled mainly by screening the titanium-based raw material and controlling the introduction of impurities in the preparation process as much as possible.
In some further preferred embodiments of the present invention, in step S1, the titanium-based material is a titanium material with a model number TA 1.
Due to the difference of the activity of iron and titanium metal, when the titanium-based raw material contains a trace element Fe, Fe is enriched at a grain boundary part in the multi-step heat treatment process, so that the efficiency of the microcell formed by other parts of the titanium-based raw material and the Fe at the grain boundary part is further improved, and the formation of a honeycomb-shaped pore structure is facilitated.
When the impurity content in the titanium-based raw material is too low, the uniformity of the grain structure in the titanium-based raw material is difficult to control, and the grain size is relatively large, so that the shape difference of the etched honeycomb-shaped pore structure is large; when the impurity content is high, large holes are formed in etching due to segregation and aggregation of elements such as Fe, C and O, the honeycomb-shaped hole structure is difficult to form, and the mechanical property of the honeycomb-shaped hole structure is difficult to guarantee. That is, although the titanium-based raw material having the composition ratio out of the above range can also obtain a corresponding honeycomb cell structure, if the composition ratio of the titanium-based raw material falls within the above range, the uniformity of the obtained honeycomb cell structure, and the degree of the significance of the honeycomb cell structure are optimal. In addition, the impurity content in the titanium-based raw material is controlled, so that the function of regulating and controlling the mechanical property of the obtained titanium-based material can be achieved.
In conclusion, the control of the components of the titanium-based material has the effects of regulating and controlling the internal organization and performance of the obtained titanium-based material, optimizing the micro-morphology of the titanium-based material after subsequent acid etching and accurately obtaining the honeycomb-shaped pore structure.
In some embodiments of the present invention, in step S1, the titanium-based raw material has a thickness of 0.5-2.0 mm.
In some embodiments of the invention, in step S1, the titanium-based feedstock has a maximum face dimension of 50 x 50 mm.
In some embodiments of the present invention, in step S1, the titanium-based raw material is obtained by: and cutting into specific sizes by using a cutting machine.
In some embodiments of the present invention, step S1 further comprises cleaning the titanium-based raw material before the multi-step heat treatment.
In some embodiments of the invention, cleaning the titanium-based feedstock comprises sequentially: and using acetone as a medium, ultrasonically cleaning to remove oil stains on the surface of the titanium-based raw material, then washing the surface of the titanium-based raw material with deionized water, and drying for later use.
In some embodiments of the invention, in step S1, the titanium-based feedstock is a cold rolled titanium-based feedstock that has not been annealed.
In some embodiments of the present invention, in step S1, the two-step heat treatment, the first heat treatment, the constant temperature is 500-.
In some embodiments of the invention, the first heat treatment is performed at a constant temperature for 30-60 min.
After the first heat treatment, the temperature is directly raised without being reduced, and the second heat treatment is carried out.
In some embodiments of the present invention, the constant temperature of the second heat treatment is 570-.
In some embodiments of the invention, the second heat treatment is performed at a constant temperature for 20-40 min.
In some embodiments of the present invention, step S1 further includes air cooling the obtained titanium-based raw material after the multi-step heat treatment, so as to achieve the purpose of rapid cooling.
Because the titanium-based material adopted by the invention is a cold-rolled titanium material, and the crystal grains in the cold-rolled titanium material are completely rolled and crushed, corresponding heat treatment is carried out before etching to obtain equiaxed crystal grains and improve the mechanical property of the obtained titanium-based material.
In some embodiments of the invention, in the step S2, the source of the ferrous ions in the etching solution includes at least one of ferrous sulfate, ferrous nitrate and ferrous chloride.
Ferrous sulfate, ferrous nitrate and ferrous chloride may all function to form a honeycomb-shaped pore structure, but in the present invention, the most preferred source of ferrous ions is ferrous sulfate, in view of the principle of introducing as few impurity ions as possible.
In some embodiments of the invention, in step S2, the etching solution further includes an acid.
In some embodiments of the invention, the source of acid in the etching solution comprises at least one of sulfuric acid, hydrochloric acid and oxalic acid.
In some embodiments of the invention, in the step S2, the raw material of the etching solution includes 20% to 40% of H by mass percentage2SO45% -10% of FeSO4And the balance being water.
Sulfuric acid, hydrochloric acid, oxalic acid and the like can be selected as the etching liquid of the titanium-based material, wherein the oxalic acid is an organic weak acid, the etching time is longer, the reaction temperature is higher, and the oxalic acid is unstable and is heated and easily decomposed to generate toxic gas to pollute the environment; the hydrochloric acid is non-oxidizing strong acid, when a thicker compact oxide layer, namely titanium oxide, is generated on the surface of the titanium matrix, the hydrochloric acid is difficult to dissolve the oxide layer, and further the etching reaction with the titanium matrix is influenced; the sulfuric acid is an oxidizing acid, can react with titanium oxide, has lower etching cost and easier recycling of waste acid, can prolong the etching effect of the sulfuric acid by increasing the temperature, and is beneficial to reducing the acid consumption and the production cost. In summary, although sulfuric acid, hydrochloric acid and oxalic acid can be used as the acid in the etching solution, the most preferable source of the acid in the present invention is sulfuric acid in order to improve the etching efficiency, reduce the production cost and reduce the introduction of impurity ions.
In some embodiments of the present invention, the acid etching is performed at a temperature of 60-85 ℃ in step S2.
In some embodiments of the present invention, in step S2, the acid etching time is 90-150 min.
In some embodiments of the present invention, in step S2, the acid etching, temperature control, and water bath process control are performed.
The principle of the acid etching is shown in formulas (1) to (3):
TiO2+2H2SO4→Ti(SO4)2+2H2O (1)；
2Ti+3H2SO4→Ti2(SO4)3+3H2↑ (2)；
Ti+H2→TiH2 (3)。
specifically, the principle of the acid etching is as follows: firstly, an oxide layer on the surface of the titanium-based raw material reacts with sulfuric acid in etching liquid to generate titanium sulfate, the titanium oxide is more corrosion-resistant, the reaction needs to be carried out at a higher temperature, a shallow layer is etched on the surface of the titanium-based raw material after the step, a crystal boundary is exposed, and due to the action of multi-step heat treatment, the content of Fe at the crystal boundary is greater than that in the crystal, and the Fe and Ti form micro-galvanic corrosion, so that the corrosion rate at the crystal boundary is greater than that in the crystal; the titanium matrix reacts with dilute sulfuric acid to generate titanium sulfate and generate a large amount of hydrogen, ferrous ions and hydrogen ions in the solution are enriched at the grain boundary, so that the corrosion rate at the grain boundary is further accelerated, and the etching rate at the grain boundary is further accelerated due to the continuous reaction of the hydrogen in the solution; the titanium substrate absorbs hydrogen to form a thin layer of titanium hydride on the surface of the titanium substrate, and the whole titanium substrate has a honeycomb-shaped pore structure on the surface of the obtained titanium substrate.
In some embodiments of the present invention, step S2 further includes, after the acid etching, sequentially rinsing the obtained titanium-based material with deionized water and alcohol, and performing vacuum drying.
In conclusion, in the titanium-based material preparation method provided by the invention, a stable (high test reproducibility and uniform cellular pore structure) cellular pore structure is obtained by double control of the titanium-based raw material and the etching solution; by controlling the impurity content of the titanium-based raw material and the multi-step heat treatment process, uniform equiaxial grain structure is obtained, and the mechanical property of the obtained titanium-based material is improved.
According to a further aspect of the present invention, an implant made of the titanium-based material is provided.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) the surface of the titanium-based material is provided with a honeycomb-shaped pore structure, so that the roughness and the specific surface area of the surface of the titanium-based material are increased, and if the implant is coated with an active coating on the surface of the titanium-based material, the adhesive force of the coating can also be increased.
(2) The titanium-based material has larger specific surface area, roughness, hydrophilicity and the like, can increase the stability and the bone combination rate of the implant at the initial stage of implantation, promotes the formation of new bones, and shortens the healing time.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view showing the shape of a titanium-based material obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a titanium-based material obtained in example 1 of the present invention;
FIG. 3 is an SEM image of a titanium-based material obtained in example 1 of the present invention;
FIG. 4 is an SEM image of a titanium-based material obtained in example 2 of the present invention;
FIG. 5 is an SEM image of a titanium-based material obtained in example 3 of the present invention;
FIG. 6 is an SEM image of a titanium-based material obtained in comparative example 1 of the present invention;
FIG. 7 is an SEM image of a titanium-based material obtained in comparative example 2 of the present invention;
FIG. 8 is an SEM image of a titanium-based material obtained in comparative example 3 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If there is a description of first and second for the purpose of distinguishing technical features only, this is not to be understood as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of technical features indicated.
Example 1
The embodiment prepares the titanium-based material, and the specific process comprises the following steps:
D1. selecting a titanium-based raw material, wherein the titanium-based raw material is an unannealed cold-rolled titanium material with the model number of TA1, and the composition of the cold-rolled titanium material is shown in Table 1:
TABLE 1 composition of titanium-based raw material used in example 1
D2. Cleaning a titanium-based raw material: taking acetone as a medium, ultrasonically cleaning to remove oil stains on the surface of the titanium-based raw material, then washing the surface of the titanium-based raw material with deionized water, and drying for later use;
D3. carrying out multi-step heat treatment on the titanium-based raw material, wherein the specific treatment conditions are as follows:
firstly heating to 520 ℃, and preserving heat for 30 min; directly raising the temperature to 580 ℃ again without cooling, and preserving the temperature for 30 min; then air cooling is carried out;
D4. preparing an etching solution: in the etching solution, the raw material comprises 25% of H2SO48% of FeSO4The balance being water;
D5. acid etching: heating the etching solution obtained in the step D4 to 70 ℃ in a water bath; and D3, placing the titanium-based raw material obtained in the step D3 in the heated etching solution, standing for 100min, taking out, sequentially and respectively washing the obtained titanium-based material with deionized water and alcohol, and storing after vacuum drying in a drying box to obtain the titanium-based material.
Example 2
In this example, a titanium-based material was prepared, which is specifically different from that in example 1 in that:
(1) in step D1, the titanium-based starting material was of different types and the specific composition was as shown in Table 2.
TABLE 2 compositional composition of titanium-based raw material used in example 2
Example 3
In this example, a titanium-based material was prepared, which is specifically different from that in example 1 in that:
(1) in step D1, the titanium-based starting material was of different types and the specific composition was as shown in Table 2.
TABLE 3 compositional composition of titanium-based raw material used in example 3
Comparative example 1
This comparative example prepared a titanium-based material, which differs from example 1 in that:
(1) in step D4, the etching solution does not include FeSO4。
Comparative example 2
This example prepared a titanium-based material, differing from example 1 in that:
(1) step D3 is not carried out, that is, the titanium-based raw material cleaned in step D2 is directly put into the etching solution obtained in step D4 for etching.
Comparative example 3
This example prepared a titanium-based material, differing from example 1 in that:
(1) in step D3, only one-step heat treatment was performed, not multi-step heat treatment (corresponding to the two-step heat treatment in example 1); the specific heat treatment parameters are as follows: treating at 580 deg.C for 60 min.
Test examples
The test examples test the properties of the titanium-based materials prepared in the examples and comparative examples. Wherein:
the morphology was obtained by scanning electron microscopy, specifically:
example 1 the titanium-based material obtained is schematically shown in fig. 1, and functions as a base body of an implant, wherein the dark color part is a base body formed of a titanium-based material, and white circular holes are used for fixing the base body to bone. SEM images of the titanium-based material obtained in example 1 are shown in FIGS. 2 to 3; the SEM image of the titanium-based material obtained in example 2 is shown in FIG. 4; the SEM image of the titanium-based material obtained in example 3 is shown in FIG. 5; the SEM image of the titanium-based material obtained in comparative example 1 is shown in fig. 6; the SEM image of the titanium-based material obtained in comparative example 2 is shown in fig. 7; the SEM image of the titanium-based material obtained in comparative example 3 is shown in fig. 8.
As can be seen from the SEM image, the surface of the titanium-based material prepared by the preparation method provided by the invention has a honeycomb-shaped pore structure, and the grain size of the titanium-based material in the area where the honeycomb-shaped pore structure is located is 10-100 mu m; the honeycomb-shaped pore structure has a pore diameter of 0.1 to 5 μm (measured in SEM images). When the titanium-based composite porous titanium-based implant is applied to an implant, the adhesive force between the titanium-based material and an active coating formed on the surface of the titanium-based material can be improved, and meanwhile, the porous rough structure can also increase the stability and the bone bonding rate of the implant at the initial stage of implantation, promote the formation of new bones and shorten the healing time.
As can be seen from comparison between fig. 2 to 3 and fig. 4 to 5, in examples 2 to 3, the morphology of the honeycomb-shaped pore structure of the obtained titanium-based material has changed to a certain extent due to adjustment of the impurity content, and the uniformity or the apparent degree thereof is slightly worse than that in example 1, but the titanium-based material still has the honeycomb-shaped pore structure, and can still meet the requirements of the implant on the titanium-based material.
As can be seen from the comparison between FIGS. 2-3 and FIG. 6, if the etching solution prepared in step D4 does not include FeSO4The honeycomb-shaped pore structure cannot be formed, but a crack-shaped morphology is formed, and when the titanium-based material with the morphology is used for the implant, the performance of the implant is reduced.
As is clear from comparison of fig. 2 to 3 with fig. 7, the honeycomb-shaped cell structure having distinct grain boundaries cannot be formed without the heat treatment of step D3, and the specific surface area is further reduced as compared with example 1.
As is clear from comparison of fig. 2 to 3 with fig. 8, if the heat treatment is performed in only one step, the crystal grain size of the obtained honeycomb-shaped cell structure portion becomes too large to satisfy the use requirement.
In conclusion, from the surface appearance of the obtained titanium-based material, the obtained titanium-based material can obtain the surface with a honeycomb-shaped pore structure with uniform and moderate grain size within the range provided by the invention.
The mechanical properties of the titanium-based materials obtained in example 1 and comparative example 3 were also characterized in the test examples by reference to American Standard ASTM B265, and the test results are shown in Table 3.
TABLE 3 mechanical Properties of the titanium-based materials obtained in example 1 and comparative example 3
The results in table 3 show that the titanium-based material obtained by the one-step heat treatment (comparative example 3) is reduced in tensile strength, yield strength, elongation and grain size, compared to the two-step heat treatment (example 1), because: one-step heat treatment, if the temperature is too low, recrystallization cannot be finished; the temperature is too high, and the grain structure is coarse. The results also show that the multi-step heat treatment has the functions of obtaining equiaxed grain structures with uniform sizes and moderate sizes, reducing anisotropy, obtaining better mechanical properties and adjusting crystallization.
From the above results, it is demonstrated that the mechanical properties and surface structure of the obtained titanium-based material are all optimized by defining the raw material components, the number of heat treatment steps, and the acid etching solution components (example 1).
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (15)
1. A titanium-based material, characterized in that the surface of the titanium-based material has a honeycomb-shaped pore structure;
the aperture of the honeycomb-shaped pore structure is 0.1-5 mu m, and crystal grains with the grain diameter of 10-100 mu m are distributed in the titanium-based material;
the preparation method of the titanium-based material comprises the following steps:
s1, carrying out two-step heat treatment on a titanium-based raw material;
s2, carrying out acid etching on the titanium-based raw material obtained in the step S1 by using an etching solution, wherein the etching solution contains ferrous ions.
2. The titanium-based material of claim 1, wherein the titanium-based material is enriched with Fe at grain boundaries.
3. The titanium-based material of claim 1, wherein in step S1, the titanium-based material comprises, in mass percent:
Fe 0.02-0.05%；
C 0.01-0.03%；
O 0.03-0.10%；
the balance being Ti.
4. The titanium-based material of claim 1, wherein in step S1, said titanium-based material further comprises N, H, Al and other impurity elements.
5. The titanium-based material according to claim 4, wherein the content of a single impurity element is less than or equal to 0.04% by mass of the titanium-based raw material.
6. The titanium-based material according to claim 4, wherein the total content of impurity elements is less than or equal to 0.2%.
7. The titanium-based material as claimed in claim 1, wherein in step S1, the constant temperature of the two-step heat treatment, the first-step heat treatment, is 500-550 ℃.
8. The titanium-based material according to claim 7, wherein the first heat treatment is performed at a constant temperature for 30-60 min.
9. The titanium-based material as claimed in claim 1, wherein in step S1, the constant temperature of the two-step heat treatment and the second-step heat treatment is 570-610 ℃.
10. The titanium-based material according to claim 9, wherein the second heat treatment is performed at a constant temperature for 20-40 min.
11. The titanium-based material of claim 1, wherein in step S2, the source of ferrous ions in the etching solution includes at least one of ferrous sulfate, ferrous nitrate, and ferrous chloride.
12. The titanium-based material of claim 11, wherein in step S2, the etching solution comprises 20-40% H by mass as a raw material2SO45% -10% of FeSO4And the balance being water.
13. The titanium-based material of claim 1, wherein in step S2, said acid etching is performed at a temperature of 60-85 ℃.
14. The titanium-based material of claim 1, wherein in step S2, the acid etching is performed for 90-150 min.
15. An implant made from the titanium-based material of claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760985.8A CN113521384B (en) | 2021-07-05 | 2021-07-05 | Titanium-based material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760985.8A CN113521384B (en) | 2021-07-05 | 2021-07-05 | Titanium-based material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113521384A CN113521384A (en) | 2021-10-22 |
| CN113521384B true CN113521384B (en) | 2022-05-10 |
Family
ID=78097797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110760985.8A Active CN113521384B (en) | 2021-07-05 | 2021-07-05 | Titanium-based material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113521384B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115404481B (en) * | 2022-08-10 | 2024-04-16 | 琅泰美康医疗器械有限公司 | Preparation method of medical titanium-zirconium-based alloy microporous structure hydrophilic surface |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130085765A (en) * | 2012-01-20 | 2013-07-30 | 오스템임플란트 주식회사 | Porous surface having a triple structure of at the macro, micro and nanolevel for improving osteointegration of implants and method for producing the same |
| CN105441960A (en) * | 2014-08-22 | 2016-03-30 | 广州中国科学院先进技术研究所 | Method for constructing micrometer/nanometer hierarchical structure with super hydrophilicity on surface of titanium dental implant |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6043475A (en) * | 1983-08-19 | 1985-03-08 | Nippon Stainless Steel Co Ltd | Manufacture of titanium and titanium alloy material having superior surface etchability |
| TW214570B (en) * | 1989-06-30 | 1993-10-11 | Eltech Systems Corp | |
| CA2057373A1 (en) * | 1991-05-06 | 1992-11-07 | Donald E. Larsen, Jr. | Tia1 intermetallic articles and method of making same |
| US20070248485A1 (en) * | 2005-03-15 | 2007-10-25 | Stanley Abkowitz | Titanium face plate for cellular phone with crystalline grain texture |
| JP5062988B2 (en) * | 2005-10-19 | 2012-10-31 | 日揮触媒化成株式会社 | Novel titanium oxide and method for synthesizing novel titanium oxide |
| CN102921037B (en) * | 2012-10-31 | 2014-05-07 | 厦门大学 | Method for preparing multistage micron structure on titanium implant surface |
| TWI462757B (en) * | 2012-11-16 | 2014-12-01 | Univ Nat Taipei Technology | Method of surface treatment for titanium implant |
| CN103006339A (en) * | 2012-12-13 | 2013-04-03 | 大连理工（营口）新材料工程中心有限公司 | Preparation method of multilevel cellular structure for medical pure titanium implant surface |
| CN103243285B (en) * | 2013-05-27 | 2015-08-26 | 宁夏东方钽业股份有限公司 | A kind of tantalum tungsten material and preparation method thereof |
| CN106521466B (en) * | 2016-09-18 | 2019-06-04 | 山东大学 | The preparation method of titanium or titanium alloy surface chemical composition coating is induced using electric coupling |
| CN107215139A (en) * | 2017-06-26 | 2017-09-29 | 湖南湘投金天钛金属股份有限公司 | A kind of processing method of titanium article crystal decorative pattern |
| CN110042335B (en) * | 2019-04-11 | 2020-10-16 | 浙江大学 | Treatment process for obtaining complete recrystallization structure of titanium-zirconium alloy with low zirconium content |
| CN110170069B (en) * | 2019-05-29 | 2021-11-09 | 中国科学院金属研究所 | Medical titanium alloy material for reinforcing anchorage micro-implant and preparation method thereof |
| CN112176212B (en) * | 2020-09-25 | 2022-03-01 | 上海交通大学 | Composite material with in-situ synthesized particles and preparation method thereof |
-
2021
- 2021-07-05 CN CN202110760985.8A patent/CN113521384B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130085765A (en) * | 2012-01-20 | 2013-07-30 | 오스템임플란트 주식회사 | Porous surface having a triple structure of at the macro, micro and nanolevel for improving osteointegration of implants and method for producing the same |
| CN105441960A (en) * | 2014-08-22 | 2016-03-30 | 广州中国科学院先进技术研究所 | Method for constructing micrometer/nanometer hierarchical structure with super hydrophilicity on surface of titanium dental implant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113521384A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fattah-alhosseini et al. | Plasma electrolytic oxidation (PEO) treatment of zinc and its alloys: A review | |
| CN113521384B (en) | Titanium-based material and preparation method and application thereof | |
| He et al. | Effect of hydrothermal treatment temperature on the hydroxyapatite coatings deposited by electrochemical method | |
| JP4441642B2 (en) | Titanium cathode electrode for producing electrolytic copper foil, rotating cathode drum using the titanium cathode electrode, method for producing titanium material used for titanium cathode electrode, and method for correcting titanium material for titanium cathode electrode | |
| CN111733417A (en) | Method for low-temperature copper infiltration on surface of titanium or titanium alloy | |
| Ishizawa et al. | Thin hydroxyapatite layers formed on porous titanium using electrochemical and hydrothermal reaction | |
| CN105369340A (en) | Titanium alloy polishing method | |
| KR20230028224A (en) | Manufacturing method of magnesium alloy wire for biomedical use | |
| Dou et al. | Effect of the second-step voltages on the structural and corrosion properties of silicon–calcium–phosphate (Si–CaP) coatings on Mg–Zn–Ca alloy | |
| CN113695538A (en) | Preparation method of mirror-surface aluminum plate strip with high formability and mirror-surface aluminum plate strip | |
| Zhong et al. | Effect of minor Sc modification on the high-temperature oxidation behavior of near-α Ti alloy | |
| JPH0382745A (en) | Production of hard aluminum alloy sheet excellent in corrosion resistance | |
| Rios et al. | Self-organized TiO2 nanotubes on Ti-Nb-Fe alloys for biomedical applications: Synthesis and characterization | |
| CN110669962B (en) | Degradable biomedical Zn-Al-Mg-Nd zinc alloy and preparation method thereof | |
| CN108166044A (en) | A kind of method of the regulation and control medical TC4 titanium alloy surfaces tube diameters of 3D printing | |
| Wen et al. | Surface evolution of a gradient structured Ti in hydrogen peroxide solution | |
| CN112914762B (en) | Surface treatment process for titanium alloy dental implant | |
| CN112575272B (en) | Improved titanium cup surface crystallization treatment method | |
| CN111467577B (en) | Medical metal bone implant material | |
| JPH02146718A (en) | Manufacture of aluminum material for electrolytic capacitor electrode | |
| Wang et al. | Effect of potassium fluotitanate concentration on the corrosion resistance and degradation property of micro-arc oxidized ZM21 magnesium alloys | |
| CN1942984B (en) | Aluminum material, method of manufacturing aluminum material , electrolytic capacitor and anode material | |
| JP2008266746A (en) | Aluminum foil for electrolytic capacitor and its manufacturing method | |
| KR102150326B1 (en) | Method for surface treatment of biocompatible affinity metal material | |
| Cremasco et al. | Application of coupled substrate aging and TiO 2 nanotube crystallization heat treatments in cold-rolled Ti–Nb–Sn alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |