CN111139480A - 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
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- CN111139480A CN111139480A CN202010051199.6A CN202010051199A CN111139480A CN 111139480 A CN111139480 A CN 111139480A CN 202010051199 A CN202010051199 A CN 202010051199A CN 111139480 A CN111139480 A CN 111139480A
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- 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
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- 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
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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: 30-50 parts of sulfuric acid; 0.01-5 parts of a fluorine compound; 1-5 parts of a complexing agent; 1-5 parts of a surfactant; 1-5 parts of stabilizer and 50-100 parts of water. The technical scheme of the invention can solve the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching solution in the related technology.
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. In the related art, the acid etching solution used in the acid etching treatment is usually a mixed acid of hydrochloric acid and sulfuric acid, so that when the acid etching solution is prepared, a large amount of acid gas is often generated due to the volatility of hydrochloric acid, the environment is polluted, and the health of operators is damaged.
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. Aims to solve the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of acid etching liquid in the related technology.
In order to achieve the purpose, the acid etching solution provided by the invention comprises the following components in parts by weight: 30-50 parts of sulfuric acid; 0.01-5 parts of a fluorine compound; 1-5 parts of a complexing agent; 1-5 parts of a surfactant; 1-5 parts of stabilizer and 50-100 parts of water.
Optionally, the fluorine compound is hydrofluoric acid or a fluorine-containing salt.
Optionally, the mass fraction of the hydrofluoric acid or the fluorine-containing salt is 40% -60%.
Optionally, the complexing agent is selected from at least one of ethylenediamine tetraacetic acid, phosphate, aminocarboxylate, and organophosphonate; and/or the surfactant is selected from at least one of sodium dodecyl sulfate, ethylene glycol n-butyl ether and fatty glyceride; and/or the stabilizer is at least one selected from sulfamic acid, ammonium bicarbonate, ethylenediamine and triethanolamine.
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:
and placing the titanium implant in the acid etching solution, and carrying out ultrasonic treatment for 30-600 min.
Optionally, before the step of placing the pretreated titanium implant in the acid etching solution for acid etching treatment, the method further comprises:
and cleaning the surface of the titanium implant to be subjected to acid etching by adopting steam to remove oil stains on the surface.
Optionally, 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 liquid takes sulfuric acid as a main system, and is etched by combining a fluorine compound, wherein the fluorine compound is used as a fluorine ion source, the fluorine ion source is equivalent to hydrofluoric acid in an acid solution, and trace hydrofluoric acid can be activated to carry out acid etching operation and can replace hydrochloric acid in related technologies, so that 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 when the acid etching liquid is prepared. Meanwhile, the complexing agent is added to adjust the etching speed, so that the surface quality of the etched titanium implant is ensured to be good, and the service life of the acid etching solution is prolonged. And moreover, 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 stabilizer is added to ensure that the acid etching operation is carried out more stably, so that the surface quality of the titanium implant subjected to the acid etching treatment is further ensured to be better.
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 comprises the following components in parts by weight: 30-50 parts of sulfuric acid; 0.01-5 parts of a fluorine compound; 1-5 parts of a complexing agent; 1-5 parts of a surfactant; 1-5 parts of stabilizer and 50-100 parts of water.
The sulfuric acid is used as a main component, the fluorine compound is used as a fluorine ion source, the fluorine ion source is equivalent to hydrofluoric acid in an acid solution, and trace hydrofluoric acid can be activated to carry out acid etching operation, so that hydrochloric acid in the related technology can be replaced, acid mist is not easily volatilized when the acid etching solution is prepared, and the problems of environmental pollution and harm to the health of operators caused by volatile acid gas of the acid etching solution in the related technology are effectively avoided. The complexing agent mainly plays a role in adjusting the etching speed, ensures that the surface quality of the etched titanium implant is good, can be quickly adsorbed to the surface of the titanium implant, ensures that the acid etching operation is carried out stably, can improve the stability of the acid etching solution, and prolongs the service life of the acid etching solution. 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. 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. The stabilizer mainly plays a role in stabilizing the acid etching operation and ensures that the acid etching operation is carried out more stably, thereby further ensuring that the titanium implant subjected to the acid etching treatment has better surface quality.
It should be noted that, when preparing the acid etching solution, the amount of each component is selected to be appropriate 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, 35 parts, 40 parts, 45 parts or 50 parts by weight; the content of the fluorine compound is 0.01 part, 0.1 part, 0.5 part, 1.5 parts, 3 parts or 5 parts; the content of the complexing agent is 1 part, 2 parts, 3 parts or 5 parts; the content of the surfactant is 1 part, 2 parts, 3 parts or 5 parts; and the content of the stabilizer is 1 part, 2 parts and 3 parts
Or 5 parts; 50 parts of water, 60 parts of water, 70 parts of water, 80 parts of water, 90 parts of water or 100 parts of water.
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 is etched by combining a fluorine compound, wherein the fluorine compound is taken as a fluorine ion source, the fluorine ion source is equivalent to hydrofluoric acid in an acid solution, and a trace amount of hydrofluoric acid can be activated to carry out acid etching operation 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. Meanwhile, the complexing agent is added to adjust the etching speed, so that the surface quality of the etched titanium implant is ensured to be good, and the service life of the acid etching solution is prolonged. And moreover, 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 stabilizer is added to ensure that the acid etching operation is carried out more stably, so that the surface quality of the titanium implant subjected to the acid etching treatment is further ensured to be better.
Optionally, the fluorine compound is hydrofluoric acid or a fluorine-containing salt. Both hydrofluoric acid and fluoride containing salts can be used as fluoride ion sources here, and both can be used in conjunction with sulfuric acid for acid etching operations. When the fluorine compound is used, one or more kinds of the fluorine compound may be used in combination. The fluorine-containing salt mainly provides fluorine ions and can react with sulfuric acid to generate hydrofluoric acid, namely, the hydrofluoric acid is equivalent to hydrofluoric acid contained in the acid etching solution, and the hydrofluoric acid has high activity, so that trace hydrofluoric acid can be activated to carry out acid etching reaction, and the material cost can be saved.
Optionally, the mass fraction of hydrofluoric acid or fluoride salt is 40% -60%. When preparing the acid etching solution, the concentration of hydrofluoric acid or fluorine-containing salt is strictly controlled to ensure good etching performance. Typically, the mass fraction of hydrofluoric acid or fluoride salt is 40%, 50% or 60%.
It should be noted that, the concentration of hydrofluoric acid is not high, and when preparing the acid etching solution, the volatilization and escape of acid gas can be effectively avoided, thereby improving the operation environment. And when hydrofluoric acid is used for etching, heating operation is not needed, and the etching can be carried out at normal temperature, so that the operation is simplified.
Similarly, when preparing the etching solution, the concentration of sulfuric acid is strictly controlled to ensure good etching performance. Typically, the mass fraction of sulfuric acid is 50% to 80%, i.e. 50%, 60%, 70% or 80%.
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, the acid etching rate can be regulated after the complexing agents are added, the acid etching operation is ensured to be carried out stably, the stability of the acid etching solution is ensured to be improved, the service life of the acid etching solution is prolonged, and one or more of the complexing agents can be selected when the complexing agents are selected.
Optionally, the surfactant is selected from at least one of sodium dodecyl sulfate, ethylene glycol n-butyl ether 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 stabilizer is selected from at least one of sulfamic acid, ammonium bicarbonate, ethylenediamine and triethanolamine. The sulfamic acid, the ammonium bicarbonate, the ethylenediamine and the triethanolamine can ensure that the acid etching operation is carried out more stably, so that the surface quality of the titanium implant subjected to acid etching treatment is further ensured to be better. When the stabilizer is selected, one or more of the above-mentioned components may be used in combination.
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, and can more effectively ensure 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 are used as cleaning dispersants, so that the cleaning effect on the surface of the titanium implant can be achieved, and the surface quality of the acid-etched titanium implant can be guaranteed to be good. 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, pits and the like.
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.
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 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.
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 can be carried out at normal temperature, the operation is simple, and the cost is lower. 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 fluorine compound is used as a fluoride 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 operating 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 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 temperature is generally normal temperature, compared with the high-temperature operation when hydrochloric acid is adopted, the operation condition is reduced, and the operation cost is saved.
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.
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, 0.01 part of 40% hydrofluoric acid, 3 parts of ethylenediamine tetraacetic acid, 2 parts of sodium dodecyl sulfate, 3 parts of sulfamic acid and 50 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 normal temperature, 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%, 0.04 part of fluoride-containing salt with the mass fraction of 50%, 2 parts of phosphate, 4 parts of ethylene glycol n-butyl ether, 3 parts of ethylenediamine, 3 parts of alkyl sulfonate, 2 parts of amino tetrazole compound, 3 parts of dimethylformamide, 2 parts of butynediol and 65 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 normal temperature, 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: 50 parts of sulfuric acid with the mass fraction of 60%, 0.2 part of hydrofluoric acid with the mass fraction of 60%, 2 parts of organic phosphonate, 2 parts of ethylene glycol n-butyl ether, 3 parts of sulfamic acid and 4 parts of succinate, 3 parts of cyclohexanediamine acetic acid, 4 parts of methyl propylene glycol, 3.5 parts of pyridine and 70 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 normal temperature, 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: 45 parts of sulfuric acid with the mass fraction of 70%, 0.15 part of fluoride-containing salt with the mass fraction of 60%, 3 parts of organic phosphonate, 4 parts of sodium dodecyl sulfate, 3 parts of triethanolamine, 3 parts of alkyl sulfonate, 4 parts of amino tetrazole compound, 3 parts of acetamide, 4.5 parts of butynediol and 65 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 normal temperature, 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: 40 parts of sulfuric acid with the mass fraction of 80%, 0.3 part of hydrofluoric acid with the mass fraction of 50%, 5 parts of ethylene diamine tetraacetic acid, 3 parts of ethylene glycol n-butyl ether, 5 parts of sulfamic acid, 4 parts of alkyl sulfonate, 3 parts of cyclohexanediamine acetic acid, 4 parts of pentaerythritol, 2.5 parts of butynediol and 80 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 normal temperature, 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 acid etching treatment in examples 1 to 5 were all formed with microstructures, that is, depressed structures with pore diameters ranging from 10 to 200 μm were formed on the surfaces, honeycomb structures with pore diameters ranging from 50 to 400 nm were formed in the depressed structures, and nanotubes with diameters ranging from 50 to 100 nm were formed in the honeycomb structures. The titanium implant after acid etching has good quality through observation. And when the acid etching solution is prepared, a large amount of acid gas is not volatilized, the operation environment is improved, the acid etching operation can be carried out at normal temperature, the operation cost is saved, and the operation is simpler.
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 (10)
1. An acid etching solution is applied to acid etching treatment of titanium implants, and is characterized by comprising the following components in parts by weight:
30-50 parts of sulfuric acid;
0.01-5 parts of a fluorine compound;
1-5 parts of a complexing agent;
1-5 parts of a surfactant;
1-5 parts of a stabilizer; and
50-100 parts of water.
2. The acid etching solution according to claim 1, wherein the fluorine compound is hydrofluoric acid or a fluorine-containing salt.
3. The acid etching solution of claim 2, wherein the mass fraction of the hydrofluoric acid or the fluorine-containing salt is 40% to 60%.
4. The acid etching solution of claim 1, wherein the complexing agent is selected from at least one of ethylenediaminetetraacetic acid, phosphates, aminocarboxylates, and organophosphonates;
and/or the surfactant is selected from at least one of sodium dodecyl sulfate, ethylene glycol n-butyl ether and fatty glyceride;
and/or the stabilizer is at least one selected from sulfamic acid, ammonium bicarbonate, ethylenediamine and triethanolamine.
5. The etching solution according to any one of claims 1 to 4, further comprising 1 to 5 parts by weight of a detergent dispersant.
6. The etching solution according to claim 5, wherein the detergent dispersant is at least one selected from the group consisting of alkylsulfonic acid salts, succinimides, and succinates.
7. An acid etching method for a titanium implant is characterized by comprising the following steps:
preparing an acid etching solution according to any one of claims 1 to 6;
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.
8. The method for acid-etching a titanium implant according to claim 7, wherein the step of acid-etching the pretreated titanium implant in the acid-etching solution comprises:
and placing the titanium implant in the acid etching solution, and carrying out ultrasonic treatment for 30-600 min.
9. The method for acid etching a titanium implant according to claim 7, further comprising, before the step of placing the pretreated titanium implant in the acid etching solution for acid etching:
and cleaning the surface of the titanium implant to be subjected to acid etching by adopting steam to remove oil stains on the surface.
10. The method for acid etching a titanium implant according to any one of claims 7 to 9, further comprising, after the steps of taking out the acid-etched titanium implant, washing and drying:
and aging the acid etching solution subjected to acid etching, and filtering to obtain titanium dioxide and a recycled acid etching solution.
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| 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 |
| CN113394400A (en) * | 2021-05-26 | 2021-09-14 | 天能电池集团股份有限公司 | Negative pole diachylon and negative plate of lead storage battery and lead storage battery |
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| CN113394400A (en) * | 2021-05-26 | 2021-09-14 | 天能电池集团股份有限公司 | Negative pole diachylon and negative plate of lead storage battery and lead storage battery |
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| CN111139480B (en) | 2022-03-29 |
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