CN111235577B - Acid etching solution and acid etching treatment method of titanium implant - Google Patents
Acid etching solution and acid etching treatment method of titanium implant Download PDFInfo
- Publication number
- CN111235577B CN111235577B CN202010058402.2A CN202010058402A CN111235577B CN 111235577 B CN111235577 B CN 111235577B CN 202010058402 A CN202010058402 A CN 202010058402A CN 111235577 B CN111235577 B CN 111235577B
- Authority
- CN
- China
- Prior art keywords
- acid etching
- parts
- titanium implant
- etching solution
- acid
- 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
Classifications
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses an acid etching solution and an acid etching treatment method of a titanium implant. Wherein, the acid etching solution comprises the following components in parts by weight: 30-80 parts of sulfuric acid; 5-40 parts of chloride; 1-5 parts of a surfactant; 1-5 parts of corrosion inhibitor; and 20-60 parts of water. The technical scheme of the invention can improve the surface quality of the titanium implant obtained after the treatment of the acid etching process.
Description
Technical Field
The invention relates to the technical field of surface treatment of titanium implants, in particular to an acid etching solution and an acid etching treatment method of a titanium implant.
Background
At present, titanium implants (such as dental implants, intra-osseous implants, etc.) are mainly made of pure titanium or titanium alloys and are provided with a microstructure by means of a sand blasting process and an acid etching process to improve the surface roughness. The titanium implant surface quality obtained after the acid etching process in the related art is often poor.
The above is only for the purpose of assisting understanding of the technical aspects of the present invention, and does not represent an admission that the above is prior art.
Disclosure of Invention
The invention mainly aims to provide an acid etching solution and an acid etching treatment method of a titanium implant. Aiming at improving the surface quality of the titanium implant obtained after the treatment of the acid etching process.
In order to achieve the purpose, the acid etching solution provided by the invention comprises the following components in parts by weight: 30-80 parts of sulfuric acid; 5-40 parts of chloride; 1-5 parts of a surfactant; 1-5 parts of corrosion inhibitor; and 20-60 parts of water.
Optionally, the chloride salt is at least one of titanium chloride, sodium chloride and calcium chloride.
Optionally, the mass fraction of the sulfuric acid is 50% -98%; and/or 40-60% of chlorine salt solution or solid salt.
Optionally, the surfactant is selected from at least one of sodium dodecyl sulfate, ethylene glycol n-butyl ether and fatty glyceride; and/or the corrosion inhibitor is selected from at least one of nitrite, organic heterocyclic corrosion inhibitor, organic phosphonic acid and polyethylene.
Optionally, the acid etching solution further contains 1-5 parts by weight of a complexing agent.
Optionally, the complexing agent is selected from at least one of ethylenediamine tetraacetic acid, phosphates, aminocarboxylates, and organophosphonates.
Optionally, the acid etching solution further comprises 1-5 parts by weight of a detergent dispersant.
Optionally, the detergent dispersant is at least one selected from alkyl sulfonate, succinimide and succinate.
The invention also provides an acid etching method of the titanium implant, which comprises the following steps:
preparing the acid etching solution;
placing the pretreated titanium implant in the acid etching solution for acid etching treatment;
and taking out the titanium implant subjected to the acid etching treatment, and cleaning and drying the titanium implant.
Optionally, in the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment, the method comprises the following steps:
placing the titanium implant in the acid etching solution, and carrying out ultrasonic treatment at the temperature of 80-120 ℃ for 30-600 min;
and/or before the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment, the method further comprises the following steps:
cleaning the surface of the titanium implant to be subjected to acid etching by adopting steam to remove oil stains on the surface;
and/or after the steps of taking out the titanium implant subjected to the acid etching treatment, cleaning and drying, the method further comprises the following steps:
and aging the acid etching solution subjected to acid etching, and filtering to obtain titanium dioxide and a recycled acid etching solution.
According to the technical scheme, the acid etching solution takes sulfuric acid as a main system, combines chloride salt for acid etching, and is added with the surfactant, so that the surface tension of the titanium implant is reduced, the wetting effect of the acid etching solution on the surface of the titanium implant is improved, the effective etching area is increased, and the acid etching efficiency is improved. In addition, a corrosion inhibitor is added to ensure that the acid etching treatment process is carried out more slowly and stably, so that the surface quality of the titanium implant subjected to acid etching treatment is better. The chloride salt in the acid etching solution is used as a chloride ion source and can replace hydrochloric acid in the related technology, so that the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching solution can be effectively avoided when the acid etching solution is prepared.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides an acid etching solution which is applied to acid etching treatment of titanium implants.
The acid etching solution contains 30-80 parts by weight of sulfuric acid; 5-40 parts of chloride; 1-5 parts of a surfactant; 1-5 parts of corrosion inhibitor; and 20-60 parts of water.
The sulfuric acid is used as a main component, the chloride salt is mainly used for preparing chloride ions, and the chloride ions are combined with the sulfuric acid for carrying out acid etching operation, so that hydrochloric acid can be replaced, acid mist is not easy to volatilize when acid etching liquid is prepared, and the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching liquid can be effectively avoided. The surface active agent mainly reduces the surface tension of the titanium implant, improves the wetting effect of the acid etching solution on the surface of the titanium implant, increases the effective etching area and further improves the acid etching efficiency. The corrosion inhibitor mainly plays a role in inhibiting corrosion so as to ensure that the acid etching treatment process is carried out more slowly and stably, thereby ensuring that the surface quality of the titanium implant subjected to the acid etching treatment is better.
Here, the surfactant may be selected from an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant, and is not limited thereto. Similarly, the corrosion inhibitor may be selected from an oxide film type corrosion inhibitor, a deposited film type corrosion inhibitor or an absorption film type corrosion inhibitor, which is not limited herein.
When the acid etching solution is prepared, the appropriate dosage of each component is selected to ensure that the prepared acid etching solution has good performance. Generally, the content of sulfuric acid in the acid etching solution is 30 parts, 45 parts, 50 parts, 65 parts, 70 parts or 80 parts by weight; the content of the chlorine salt is 5 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts; the content of the surfactant is 1 part, 2 parts, 4 parts or 5 parts; the content of the corrosion inhibitor is 1 part, 2 parts, 4 parts or 5 parts; the water content is 20 parts, 35 parts, 40 parts, 45 parts or 60 parts.
Therefore, it can be understood that in the technical scheme of the invention, the acid etching solution takes sulfuric acid as a main system, and simultaneously the surfactant is added, so that the surface tension of the titanium implant is reduced, the wetting effect of the acid etching solution on the surface of the titanium implant is improved, the effective etching area is increased, and the acid etching efficiency is improved. In addition, a corrosion inhibitor is added to ensure that the acid etching treatment process is carried out more slowly and stably, so that the surface quality of the titanium implant subjected to acid etching treatment is better. The chloride salt in the acid etching solution is used as a chloride ion source and can replace hydrochloric acid in the related technology, so that the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching solution can be effectively avoided when the acid etching solution is prepared.
Optionally, the chloride salt is at least one of titanium chloride, sodium chloride and calcium chloride. The titanium chloride, sodium chloride and calcium chloride can decompose chloride ions after being added, can be used as a chloride ion source, can be combined with sulfuric acid for acid etching operation, and can be selected from one or more of the mixtures when chloride salt is selected.
Optionally, the mass fraction of sulfuric acid is 50% -98%. When preparing the acid etching solution, the concentration of the sulfuric acid is strictly controlled to ensure that the etching performance is good. Typically, the mass fraction of sulfuric acid is 50%, 60%, 70%, 80% or 98%.
Optionally, the chlorine salt is a 40% -60% solution or solid salt by mass fraction. When preparing the acid etching solution, the concentration of the chloride salt is strictly controlled to ensure that the etching performance is good. Typically, the mass fraction of chloride salt is 40%, 50% or 60%.
Optionally, the surfactant is selected from at least one of sodium dodecyl sulfate, ethylene glycol n-butyl ether, polyethylene glycol, and fatty glyceride. The sodium dodecyl sulfate, the ethylene glycol n-butyl ether and the fatty glyceride are all surfactants, so that the surface tension of the titanium implant can be reduced, the wetting effect of the acid etching solution on the surface of the titanium implant is improved, the effective etching area is increased, and the acid etching efficiency is improved. When a surfactant is selected, one or more of them may be selected as a mixture.
Optionally, the surfactant is sodium dodecyl sulfate, which is a stable surfactant, so that the surface tension of the acid etching solution is reduced, meanwhile, the fluidity of the acid etching solution can be improved, and the excessive etching of the titanium implant is eliminated, thereby preventing the occurrence of defects such as 'etching grooves', 'slopes' and 'ripples', and facilitating the high-precision etching.
Optionally, the surface active agent is ethylene glycol n-butyl ether, and the ethylene glycol n-butyl ether contains hydrophilic ether bonds and undissociated hydroxyl groups, so that an adsorption effect can be generated on the surface of the titanium implant, the interfacial tension is reduced, the wetting effect of the acid etching solution on the surface of the titanium implant is improved, the etching effective area is increased, and the acid etching efficiency is improved.
Optionally, the surfactant is polyethylene glycol which is used as the surfactant, the bubble capacity is strong, when the acid etching solution reacts with the titanium implant, molecules of the surfactant are directionally arranged on the surface of the solution to generate a layer of foam liquid film which is densely and uniformly covered on the liquid surface of the groove, the gas diffusion is retarded, meanwhile, the volatilization and the discharge of the acid mist can be absorbed and inhibited, and the environment is protected.
Optionally, the corrosion inhibitor is selected from at least one of nitrites, organic heterocyclic corrosion inhibitors, organic phosphonic acids, polyethylenes.
The nitrite, the organic heterocyclic corrosion inhibitor, the organic phosphonic acid and the polyethylene all play a role in inhibiting corrosion and can ensure that the acid etching treatment process is carried out more slowly and stably, thereby ensuring that the surface quality of the titanium implant subjected to the acid etching treatment is better. When the corrosion inhibitor is selected, one or more of the mixtures can be selected.
Optionally, the corrosion inhibitor is an organic heterocyclic corrosion inhibitor, the organic heterocyclic corrosion inhibitor is a thioether corrosion inhibitor and/or an azole corrosion inhibitor, the two corrosion inhibitors can form a protective film layer with a small thickness on the surface of the titanium implant, and the thermal stability of the protective film layer is good, so that the acid etching rate is reduced, and the acid etching treatment process is ensured to be performed slowly and stably.
Furthermore, the acid etching solution also contains 1-5 parts of complexing agent according to the parts by weight.
The complexing agent is added to the surface of the titanium implant, so that the surface of the titanium implant can be quickly adsorbed, the stable operation of acid etching is ensured, the stability of the acid etching solution can be improved, and the service life of the acid etching solution is prolonged.
When the acid etching solution is prepared, the dosage of the complexing agent is proper so as to more effectively ensure the service life of the acid etching solution. Typically, the complexing agent is used in an amount of 1 part, 2 parts, 4 parts, or 5 parts by weight.
Optionally, the complexing agent is selected from at least one of ethylenediaminetetraacetic acid, phosphates, aminocarboxylates, organophosphonates. The ethylene diamine tetraacetic acid, the phosphate, the aminocarboxylate and the organic phosphonate are all complexing agents, and after the complexing agents are added, the stability of the acid etching solution can be improved, the service life of the acid etching solution can be prolonged, and when the complexing agents are selected, one or more of the complexing agents can be selected.
Furthermore, the acid etching solution also contains 1-5 parts by weight of a detergent dispersant.
The addition of the cleaning dispersant can play a role in cleaning the surface of the titanium implant, so that the surface quality of the acid-etched titanium implant is better.
Optionally, the detergent dispersant is at least one selected from alkyl sulfonate, succinimide and succinate. The alkyl sulfonate, the succinimide and the succinate as the cleaning dispersant can clean the surface of the titanium implant, so that the surface quality of the titanium implant after acid etching is better. When a detergent dispersant is selected, one or more of the above dispersants may be used.
Preferably, the cleaning dispersant is selected from alkyl sulfonate, and the alkyl sulfonate can eliminate the defects of corner air channels, ripples, depressions and the like and improve the surface quality of the titanium implant.
Furthermore, the acid etching solution also contains an inhibitor which is mainly used for adjusting the acid etching rate, so that the acid etching operation is carried out more stably, the loss of the key size of the microstructure is reduced, the process profit is increased, and the etching structure with the proper taper angle is realized, so that the microstructure with the taper angle can be obtained when the titanium implant is etched. Generally, the inhibitor is one or more mixture of amino azole compound and carboxylic acid compound. The amino azole compound can be amino tetrazole compound, and the carboxylic acid compound is ethylenediamine tetraacetic acid or cyclohexanediacetic acid. In general, the inhibitor is used in an amount ranging from 1 to 5 parts by weight, such as 1 part, 2 parts, 3 parts, 4 parts, or 5 parts, in order to allow the inhibitor to exert its effect more sufficiently.
Furthermore, the acid etching solution also contains an accelerant, and the accelerant can promote the acid etching solution to quickly meet the requirements of acid etching operation, improve the acid etching rate, reduce the time of the acid etching operation and improve the efficiency of the acid etching operation. Typically, the accelerator is an amine compound and/or an alcohol compound; wherein, the amine compound is selected from at least one of formamide, dimethylformamide, acetamide, ethylenediamine and ethanolamine, and the alcohol compound is selected from at least one of glycerol, pentaerythritol, methyl propylene glycol, xylitol and sorbitol. In general, the amount of accelerator is in the range of 1 to 5 parts by weight, such as 1 part, 2 parts, 3 parts, 4 parts or 5 parts by weight, in order to allow the accelerator to exert its effect more sufficiently.
It can be understood that the acid etching solution of the present invention includes both the inhibitor and the accelerator, so that the acid etching rate can be maintained at a stable value by the action of the inhibitor and the accelerator, thereby ensuring that the acid etching operation of the titanium implant is performed more smoothly, which is beneficial to the improvement of the surface quality of the titanium implant.
Certainly, in order to keep the whole etching system stable, the etching solution of the invention also contains a stabilizer to ensure the stability of the acid etching operation, thereby further ensuring that the titanium implant subjected to the acid etching treatment has better surface quality. In general, the stabilizer can be one or more of sulfamic acid, ammonium bicarbonate, ethylenediamine and triethanolamine. In general, the amount of stabilizer is in the range of 1 to 5 parts by weight, such as 1 part, 2 parts, 3 parts, 4 parts or 5 parts by weight, in order to allow the accelerator to exert its effect more sufficiently.
Furthermore, in order to improve the surface quality of the titanium implant after acid etching, the acid etching solution also contains a leveling agent, so that the surface of the titanium implant is bright and smooth, and the surface quality is better. Generally, the leveling agent can be one or a mixture of more of butynediol, pyridine and quinoline compounds. In general, leveling agents are used in amounts ranging from 0.1 to 5 parts, such as 0.1 part, 0.5 part, 1.5 parts, 2.5 parts, 3.5 parts, 4.5 parts, or 5 parts by weight.
The invention also provides an acid etching method of the titanium implant, which comprises the following steps:
preparing the acid etching solution;
placing the pretreated titanium implant in an acid etching solution for acid etching treatment;
and taking out the titanium implant subjected to the acid etching treatment, and cleaning and drying the titanium implant.
Specifically, the components in the acid etching solution are prepared according to the proportion, the prepared acid etching solution is placed in an acid etching groove, the pretreated titanium implant is placed in the acid etching groove and subjected to acid etching treatment for a period of time, and then the acid-etched titanium implant is taken out, cleaned and dried. After the titanium implant is subjected to acid etching treatment, the titanium implant is generally rinsed and ultrasonically cleaned to remove residual stains on the surface of the titanium implant and improve the quality of the titanium implant. And by controlling the ultrasonic power and frequency of the ultrasonic cleaning operation, the problems of local oxidation discoloration and stain residue on the surface of the titanium implant after acid etching treatment can be effectively solved. Generally, the ultrasonic power range for controlling the ultrasonic cleaning operation is 1-10KW, and the ultrasonic frequency range is 10-30 KHZ.
In the preparation of the etching solution, the components are added sequentially in order to disperse the components uniformly, and the mixture is stirred while being added, so that the etching solution prepared by this method is excellent in performance and can sufficiently exhibit the functions of each component.
It can be understood that the acid etching treatment method of the titanium implant is simple to operate and low in cost. Because the acid etching solution adopts the acid etching solution of the invention, the titanium implant surface quality after the acid etching operation treatment is better, and the acid etching efficiency is higher. Meanwhile, the chloride salt is used as a chloride ion source in the acid etching solution to replace hydrochloric acid in the related technology, so that the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching solution can be effectively avoided when the acid etching solution is prepared, and the operation environment is improved.
Further, the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment comprises the following steps:
and placing the titanium implant in the acid etching solution, and carrying out ultrasonic treatment at the temperature of 80-120 ℃ for 30-600 min.
Ultrasonic treatment is adopted during acid etching operation, so that acid etching liquid can be fully contacted with the titanium implant, the effect of each component is fully exerted, and the acid etching effect is better. The operation temperature and the treatment time are strictly controlled, and the operation temperature is kept at 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃; the treatment time is controlled at 30min, 100min, 300min, 450min or 600 min.
Further, before the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment, the method further comprises the following steps:
and cleaning the surface of the titanium implant to be subjected to acid etching by adopting steam to remove oil stains on the surface.
The surface of the titanium implant is cleaned by high-temperature steam, so that the surface oil stain can be effectively removed, and the cost is low. Meanwhile, the high-temperature steam pretreatment operation is adopted, so that harmful gas is not generated, and the method is environment-friendly.
Further, after the steps of taking out the titanium implant subjected to the acid etching treatment, cleaning and drying, the method further comprises the following steps:
and aging the acid etching solution subjected to acid etching, and filtering to obtain titanium dioxide and a recycled acid etching solution.
The acid etching liquid after acid etching is recycled and regenerated, so that the resource utilization rate can be maximized, and the resource waste is avoided. In general, the acid etching solution after acid etching is aged to separate out titanium dioxide, and then the titanium dioxide and the recycled acid etching solution can be obtained by filtration, wherein the titanium dioxide can be sold as a product, and the recycled acid etching solution can be recycled to the acid etching operation. Thus, the utilization rate of resources can be maximized. It should be noted that, when the acid etching solution of the present invention contains the accelerator, the acid etching solution can be prompted to quickly meet the requirement of the acid etching operation, the acid etching rate is increased, and the time of the acid etching operation is reduced, so that the acid etching solution after acid etching can be quickly recycled and regenerated, and the obtained recycled acid etching solution can be timely and quickly added into the acid etching solution to continue the acid etching operation, such that the resource utilization rate can be more fully achieved, the cost is saved, the treatment time of the titanium implant can be shortened, and the treatment efficiency is increased.
The acid etching solution and the acid etching method of the titanium implant according to the present invention will be described in detail below with reference to specific examples.
Example 1
The acid etching solution comprises the following components in parts by weight: 30 parts of 50% sulfuric acid, 10 parts of 40% titanium chloride, 2 parts of sodium dodecyl sulfate, 3 parts of organic heterocyclic corrosion inhibitor and 25 parts of water.
Firstly, preparing the acid etching solution according to the proportion, and placing the prepared acid etching solution in an acid etching tank for later use. And simultaneously, cleaning the surface of the titanium implant to be subjected to acid etching by adopting high-temperature steam to remove surface oil stains to obtain the clean titanium implant. And then putting the clean titanium implant into acid etching liquid in an acid etching groove, carrying out ultrasonic treatment for 60min at the temperature of 80 ℃, then taking out, cleaning and drying. And finally, aging the acid etching solution subjected to acid etching, and then filtering to obtain titanium dioxide and a recycled acid etching solution.
Example 2
The acid etching solution comprises the following components in parts by weight: 45 parts of sulfuric acid with the mass fraction of 60%, 15 parts of sodium chloride with the mass fraction of 50%, 3 parts of sodium dodecyl sulfate, 3 parts of nitrite, 2 parts of ethylene diamine tetraacetic acid, 3 parts of alkyl sulfonate and 35 parts of water.
Firstly, preparing the acid etching solution according to the proportion, and placing the prepared acid etching solution in an acid etching tank for later use. And simultaneously, cleaning the surface of the titanium implant to be subjected to acid etching by adopting high-temperature steam to remove surface oil stains to obtain the clean titanium implant. And then putting the clean titanium implant into acid etching liquid in an acid etching groove, carrying out ultrasonic treatment for 80min at the temperature of 100 ℃, then taking out, cleaning and drying. And finally, aging the acid etching solution subjected to acid etching, and then filtering to obtain titanium dioxide and a recycled acid etching solution.
Example 3
The acid etching solution comprises the following components in parts by weight: 55 parts of sulfuric acid with the mass fraction of 60%, 35 parts of sodium chloride with the mass fraction of 60%, 2 parts of ethylene glycol n-butyl ether, 3 parts of nitrite, 3 parts of ethylene diamine tetraacetic acid, 4 parts of alkyl sulfonate, 3 parts of amino tetrazole compound, 2 parts of formamide, 3 parts of sulfamic acid, 2 parts of butynediol and 45 parts of water.
Firstly, preparing the acid etching solution according to the proportion, and placing the prepared acid etching solution in an acid etching tank for later use. And simultaneously, cleaning the surface of the titanium implant to be subjected to acid etching by adopting high-temperature steam to remove surface oil stains to obtain the clean titanium implant. And then putting the clean titanium implant into acid etching liquid in an acid etching groove, carrying out ultrasonic treatment for 90min at the temperature of 110 ℃, then taking out, cleaning and drying. And finally, aging the acid etching solution subjected to acid etching, and then filtering to obtain titanium dioxide and a recycled acid etching solution.
Example 4
The acid etching solution comprises the following components in parts by weight: 70 parts of sulfuric acid with the mass fraction of 70%, 40 parts of sodium chloride with the mass fraction of 60%, 3 parts of ethylene glycol n-butyl ether, 3 parts of organic heterocyclic corrosion inhibitor, 3 parts of ethylene diamine tetraacetic acid, 3 parts of succinimide, 2 parts of cyclohexanediamine acetic acid, 4 parts of methyl propylene glycol, 3 parts of ethylene diamine, 2 parts of pyridine and 55 parts of water.
Firstly, preparing the acid etching solution according to the proportion, and placing the prepared acid etching solution in an acid etching tank for later use. And simultaneously, cleaning the surface of the titanium implant to be subjected to acid etching by adopting high-temperature steam to remove surface oil stains to obtain the clean titanium implant. And then putting the clean titanium implant into acid etching liquid in an acid etching groove, carrying out ultrasonic treatment for 90min at the temperature of 100 ℃, then taking out, cleaning and drying. And finally, aging the acid etching solution subjected to acid etching, and then filtering to obtain titanium dioxide and a recycled acid etching solution.
Example 5
The acid etching solution comprises the following components in parts by weight: 80 parts of sulfuric acid with the mass fraction of 80%, 35 parts of sodium chloride with the mass fraction of 50%, 5 parts of sodium dodecyl sulfate, 3 parts of organic heterocyclic corrosion inhibitor, 5 parts of ethylene diamine tetraacetic acid, 4 parts of alkyl sulfonate, 4 parts of amino tetrazole compound, 2 parts of ethanolamine, 3 parts of sulfamic acid, 4 parts of butynediol and 55 parts of water.
Firstly, preparing the acid etching solution according to the proportion, and placing the prepared acid etching solution in an acid etching tank for later use. And simultaneously, cleaning the surface of the titanium implant to be subjected to acid etching by adopting high-temperature steam to remove surface oil stains to obtain the clean titanium implant. And then putting the clean titanium implant into acid etching liquid in an acid etching groove, carrying out ultrasonic treatment for 60min at the temperature of 110 ℃, then taking out, cleaning and drying. And finally, aging the acid etching solution subjected to acid etching, and then filtering to obtain titanium dioxide and a recycled acid etching solution.
The titanium implant surfaces subjected to the etching treatment in examples 1 to 5 were all formed with microstructures, that is, recessed structures with pore diameters ranging from 5 to 150 μm were formed on the surfaces, and honeycomb structures with pore diameters ranging from 100 to 400 nm were formed in the recessed structures, and the surface quality was good. And when the acid etching solution is prepared, a large amount of acid gas volatilization is not found, the operation environment is improved, the acid etching operation is simpler, and the cost is lower.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (2)
1. An acid etching method for a titanium implant is characterized by comprising the following steps:
preparing an acid etching solution; wherein, the acid etching solution comprises the following components in parts by weight: 30 parts of sulfuric acid with the mass fraction of 50%; 10 parts of titanium chloride with the mass fraction of 40 percent; 2 parts of sodium dodecyl sulfate; 3 parts of organic heterocyclic corrosion inhibitor; and water, 25 parts;
placing the pretreated titanium implant in the acid etching solution for acid etching treatment;
taking out the titanium implant subjected to acid etching treatment, and cleaning and drying the titanium implant; wherein, a sunken structure with the aperture range of 5-150 microns is formed on the surface of the titanium implant subjected to the acid etching treatment, and a honeycomb structure with the aperture range of 100-400 nanometers is formed in the sunken structure.
2. The method for acid etching a titanium implant according to claim 1, wherein the step of acid etching the pretreated titanium implant in the acid etching solution comprises:
placing the titanium implant in the acid etching solution, and carrying out ultrasonic treatment at the temperature of 80 ℃ for 60 min;
before the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment, the method further comprises the following steps:
cleaning the surface of the titanium implant to be subjected to acid etching by adopting steam to remove oil stains on the surface;
after the steps of taking out the titanium implant subjected to the acid etching treatment, cleaning and drying, the method further comprises the following steps:
and aging the acid etching solution subjected to acid etching, and filtering to obtain titanium dioxide and the acid etching solution for recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010058402.2A CN111235577B (en) | 2020-01-16 | 2020-01-16 | Acid etching solution and acid etching treatment method of titanium implant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010058402.2A CN111235577B (en) | 2020-01-16 | 2020-01-16 | Acid etching solution and acid etching treatment method of titanium implant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111235577A CN111235577A (en) | 2020-06-05 |
| CN111235577B true CN111235577B (en) | 2022-03-29 |
Family
ID=70878027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010058402.2A Active CN111235577B (en) | 2020-01-16 | 2020-01-16 | Acid etching solution and acid etching treatment method of titanium implant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111235577B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112391627B (en) * | 2020-11-16 | 2023-04-14 | 珠海联鼎化工设备有限公司 | Ammonia-nitrogen-free environment-friendly microetching pretreatment liquid and treatment method |
| CN113046748A (en) * | 2021-02-09 | 2021-06-29 | 佛山市安齿生物科技有限公司 | Acid etching agent for titanium alloy dental implant and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743508A (en) * | 2005-09-21 | 2006-03-08 | 中国海洋大学 | Chemical etching solution for titanium and titanium alloy |
| CN101122025A (en) * | 2007-08-09 | 2008-02-13 | 成都飞机工业（集团）有限责任公司 | Titanium alloying milling solution and milling technique used for the same |
| CN103510090A (en) * | 2013-09-03 | 2014-01-15 | 佛山科学技术学院 | Pretreatment fluids and pretreatment method for improving corrosion resistance of aluminium alloy |
| CN105288728A (en) * | 2015-11-18 | 2016-02-03 | 上海捷美生物技术有限公司 | Titanium metal osseointegration implant and titanium metal osseointegration implant surface treatment method |
| CN108950563A (en) * | 2018-07-16 | 2018-12-07 | 深圳市祺鑫天正环保科技有限公司 | Acid etching regenerates solution additive and acid etching regenerated liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602004008313T2 (en) * | 2004-12-23 | 2008-05-08 | Plus Orthopedics Ag | Surface finishing method for bone implants |
| CN104451685A (en) * | 2014-12-30 | 2015-03-25 | 哈尔滨工业大学 | Preparation method for forming second-level porous active surface structure on titanium material surface through mixed alkali |
| CN107557715A (en) * | 2017-07-27 | 2018-01-09 | 芜湖微云机器人有限公司 | Improved bioactive metal titanium implant surface modification technology |
| CN109355667A (en) * | 2018-12-05 | 2019-02-19 | 西安庄信新材料科技有限公司 | A kind of titanium surface acid washing lotion and acid cleaning process |
-
2020
- 2020-01-16 CN CN202010058402.2A patent/CN111235577B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743508A (en) * | 2005-09-21 | 2006-03-08 | 中国海洋大学 | Chemical etching solution for titanium and titanium alloy |
| CN101122025A (en) * | 2007-08-09 | 2008-02-13 | 成都飞机工业（集团）有限责任公司 | Titanium alloying milling solution and milling technique used for the same |
| CN103510090A (en) * | 2013-09-03 | 2014-01-15 | 佛山科学技术学院 | Pretreatment fluids and pretreatment method for improving corrosion resistance of aluminium alloy |
| CN105288728A (en) * | 2015-11-18 | 2016-02-03 | 上海捷美生物技术有限公司 | Titanium metal osseointegration implant and titanium metal osseointegration implant surface treatment method |
| CN108950563A (en) * | 2018-07-16 | 2018-12-07 | 深圳市祺鑫天正环保科技有限公司 | Acid etching regenerates solution additive and acid etching regenerated liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111235577A (en) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111235577B (en) | Acid etching solution and acid etching treatment method of titanium implant | |
| RU2449392C2 (en) | Gel removed by vacuum for surface cleaning, its application and method of surface decontamination | |
| CN111139480B (en) | Acid etching solution and acid etching treatment method of titanium implant | |
| JP2009014938A (en) | Resist release agent composition | |
| KR100815856B1 (en) | Echant composition for glass of flat panel display | |
| CN101381877B (en) | Method for cleaning precision parts | |
| CN106398374A (en) | Deinking method for glass workpiece and water-based deinking agent used by deinking method as well as preparation method of water-based deinking agent | |
| CN101614970B (en) | Photoresist cleaning agent composition | |
| US20040142835A1 (en) | Washing liquid for semiconductor substrate | |
| US4614607A (en) | Non-chromated deoxidizer | |
| JP2010059464A (en) | Process of manufacturing aluminum wheel | |
| CN108950565B (en) | Aluminum alloy chemical polishing agent and aluminum alloy surface polishing method | |
| WO2015023295A1 (en) | Adhesion promotion in printed circuit boards | |
| CN107346095A (en) | A kind of manufacture of semiconductor positive photoresist goes glue and application | |
| US20100147802A1 (en) | Methods and removers for removing anodized films | |
| CN111155159B (en) | Anodic oxidation liquid and coloring method of implant abutment | |
| CN113215583B (en) | Cleaning and regenerating method for aluminum and aluminum alloy device | |
| CN113820927A (en) | Positive photoresist stripping liquid composition | |
| CN102965680A (en) | Phosphorus-free oil removing process | |
| KR20190121073A (en) | Rust remover and its composition | |
| KR20110069265A (en) | Composition for desmut treatment and method of desmut treatment of aluminum alloy using the same | |
| TW200924977A (en) | Compositions and methods for wet lamination of photopolymerizable dry films onto substrates | |
| CN110003709A (en) | One kind taking off electroplating method | |
| US6126997A (en) | Method for treating magnesium die castings | |
| CN113005458A (en) | Low-corrosivity aluminum alloy chemical polishing solution |
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 |