CN103957494B - Vibrating membrane and its preparation method and application - Google Patents
Vibrating membrane and its preparation method and application Download PDFInfo
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- CN103957494B CN103957494B CN201410216590.1A CN201410216590A CN103957494B CN 103957494 B CN103957494 B CN 103957494B CN 201410216590 A CN201410216590 A CN 201410216590A CN 103957494 B CN103957494 B CN 103957494B
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Abstract
The invention provides a kind of diaphragm for loudspeaker and its preparation method and application.Specifically, the invention provides a kind of vibrating membrane, including metal base and the metal oxide layer at least one main surface of the base material, wherein, the metal oxide layer has one or more following characteristics for improving audio and/or tonequality：(i) metal oxide layer has nano-tube array structure；(ii) hardness of the metal oxide layer and/or modulus of elasticity are more than the hardness and/or modulus of elasticity of the metal base.Layer of oxide layer is directly generated by anodized technology in metallic substrate surface, the consistency and elasticity modulus of vibrating membrane can be effectively improved, improves the audio and tonequality of vibrating membrane.
Description
Technical field
The present invention relates to loudspeaker field, and in particular to a kind of vibrating membrane and its preparation method and application.
Background technology
With the development of Modern sound equipment and technology, there is higher and higher want for the high frequency diaphragm of playback system
Ask.Traditional loudspeaker vibrating diaphragm is mostly organic plastic material or its composite, and still, the voice effect of these materials is not to the utmost
Such as people's will, particularly under high pitch and high frequency sounding, tonequality is difficult to meet application demand.
At present, high pitch high frequency pronunciation field prepares vibrating membrane from titanium and its alloy material more, titanium and its alloy have compared with
Good corrosion resistance and mechanical property, it is preferable high-end metal material used for oscillation.But the frequency response model of traditional titanium vibrating membrane
Enclose narrower, sensitivity is low, and diaphagras is easily produced in high frequency, has a strong impact on its voice effect.
In summary, in the prior art, still shortage is gratifying, has wide Hz-KHz and highly sensitive high frequency
Vibrating membrane, therefore, this area can meet the high frequency diaphragm of high pitch and high frequency requirements there is an urgent need to develop.
The content of the invention
It is an object of the invention to provide a kind of vibrating membrane that disclosure satisfy that high pitch and high frequency requirements and its preparation method and application.
In the first aspect of the present invention, there is provided a kind of vibrating membrane, the vibrating membrane include metal base and positioned at institutes
The metal oxide layer at least one main surface of base material is stated, wherein, the metal oxide layer has one or more improve
The following characteristics of audio and/or tonequality：
(i) metal oxide layer has nano-tube array structure；
(ii) hardness of the metal oxide layer and/or modulus of elasticity are more than the hardness and/or bullet of the metal base
Property modulus.
In another preference, the hardness of the metal oxide layer is 4~6GPa.
In another preference, the hardness of the base material is 2~5Gpa.
In another preference, the modulus of elasticity of the metal oxide layer is 140~200GPa.
In another preference, the modulus of elasticity of the base material is 70~140Gpa.
In another preference, the metal oxide layer causes the vibrating membrane that different colors is presented.
In another preference, the substrate metal includes the metal being selected from the group：Pure titanium, titanium alloy, fine aluminium, aluminium close
Gold, or its combination.
In another preference, the metal oxide layer with nano-tube array structure includes titanium oxide and/or oxygen
Change aluminium.
In another preference, the average length of the nanotube is 1 μm~50 μm；And/or the nanotube is averaged
A diameter of 20~150nm.
In the second aspect of the present invention, there is provided a kind of loudspeaker, the loudspeaker are included described in first aspect present invention
Vibrating membrane.
In the third aspect of the present invention, there is provided a kind of preparation method of the vibrating membrane described in first aspect present invention, should
Method comprises the following steps：
(a) metal base is provided；
(b) first metal oxygen of the generation with nano-tube array structure at least one main surface of the metal base
Compound layer；
(c) nanotube of first metal oxide layer is peeled off, obtaining main surface has nano-tube array structure mould
The metal base of plate；
(d) generated on main surface of the metal base with the nano-tube array template with nano-tube array structure
Second metal oxide layer, obtain the vibrating membrane.
In another preference, the step (b) includes：
Configure the electrolyte aqueous solution containing fluorine ion；
In the electrolyte aqueous solution containing fluorine ion, using the metal base as anode, to the metal base
Anodized is carried out, so as to which generation has nano-tube array structure at least one main surface of the metal base
First metal oxide layer；
And/or the step (c) includes：
The nanotube in first metal oxide layer is peeled off by mechanical oscillation, described in the metal base
Nano-tube array template is generated on main surface, obtaining main surface has the metal base of nano-tube array structure template；
And/or the step (d) includes：
In described fluorine ion electrolyte aqueous solution, there is the metal base of the nano-tube array template with main surface
For anode, anodized is carried out to the metal base, has the second of nano-tube array structure in the main Surface Creation
Metal oxide layer, obtain the vibrating membrane.
In another preference, after the described vibrating membrane of generation, by the vibrating membrane, ultrasonic wave is clear in acetone soln
It is 5~10min to wash processing time.
In another preference, before the step of electrolyte aqueous solution of the configuration containing fluorine ion, in addition to
Lower step：
Surface preparation is carried out to the metal base.
It is described that metal base progress surface preparation is included in another preference：
Oil removing and derusting activation process are carried out to the metal base in alkali wash water；And/or
Oil removing and derusting activation process are carried out to the metal base in pickle；And/or
Ultrasonic wave cleaning is carried out to the metal base in acetone soln, then air-dried the metal base.
In another preference, the alkali wash water is sodium hydrate aqueous solution.
In another preference, the concentration of the sodium hydroxide alkali wash water is 5~20wt.%.
In another preference, the pickle includes the acid being selected from the group：Hydrofluoric acid, nitric acid or its combination.
In another preference, the volume ratio of the pickle is：Hydrofluoric acid：Nitric acid：Deionized water=0.1~10:0.4
~40:3~300.
In another preference, the electrolyte aqueous solution containing fluorine ion includes the fluoride being selected from the group：Fluorination
Ammonium, potassium fluoride, sodium fluoride or its combination；And/or
The electrolyte aqueous solution containing fluorine ion includes the additive being selected from the group：Deionized water, glycerine, second two
Alcohol, methanol or its combination.
In another preference, the fluoride is ammonium fluoride, is fluorinated in the electrolyte aqueous solution containing fluorine ion
The content of ammonium is 0.01~2.5wt.%.
In another preference, 0.2~20wt.% deionization is included in the electrolyte aqueous solution containing fluorine ion
Water.
In another preference, 0.01~99.9wt.% second is included in the electrolyte aqueous solution containing fluorine ion
Glycol.
In another preference, the anodized includes the one or more features being selected from the group：
The anodic oxidation voltage of the anodized is 5V~100V；
The oxidization time of the anodized is 20min~150min；
The electrolyte temperature of the anodized is 10 DEG C~80 DEG C；
The anodized is graphite or metal to electrode.
In the fourth aspect of the present invention, there is provided a kind of preparation method of the vibrating membrane described in first aspect present invention, should
Method comprises the following steps：
(a1) metal base is provided；
(b1) in the phosphoric acid electrolyte aqueous solution, using the metal base as anode, anode is carried out to the metal base
Oxidation processes, metal oxide layer is generated at least one main surface of the metal base, obtains the vibrating membrane.
In another preference, the metal oxide layer of generation is titanium oxide layer, and the thickness of the titanium oxide layer is
10nm~200nm.
In another preference, the anodized has the one or more features being selected from the group：
The voltage of the anodized is 5V~100V；
The oxidization time of the anodized is 5min~60min；
The electrolyte temperature of the anodized is 10 DEG C~80 DEG C；
The anodized is graphite or metal to electrode.
In another preference, the proportioning of the phosphoric acid electrolyte solution is 0.1~20wt.%H3PO4The aqueous solution, solvent
For deionized water.
It is further comprising the steps of before the step of configuration phosphoric acid electrolyte aqueous solution in another preference：
Surface preparation is carried out to the metal base.
It is described that metal base progress surface preparation is included in another preference：
Oil removing and derusting activation process are carried out to the metal base in alkali wash water；And/or
Oil removing and derusting activation process are carried out to the metal base in pickle；And/or
Ultrasonic wave cleaning is carried out to the metal base in acetone soln, then air-dried the metal base.
In another preference, the alkali wash water is sodium hydrate aqueous solution.
In another preference, the concentration of the sodium hydroxide alkali wash water is 5~20wt.%.
In another preference, the pickle includes the acid being selected from the group：Hydrofluoric acid, nitric acid or its combination.
In another preference, the volume ratio of the pickle is：Hydrofluoric acid：Nitric acid：Deionized water=0.1~10:0.4
~40:3~300.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, so as to form new or preferable technical scheme.As space is limited, exist
This no longer tires out one by one states.
Brief description of the drawings
Fig. 1 shows that what is generated in the present invention under different anodic oxidation voltages has pure titanium layer-dense oxide titanium layer knot
The vibrating membrane of structure, anodic oxidation voltage are respectively：
(a)10V、(b)30V、(c)50V；
Fig. 2 is shown on the bowl-shape nano-tube array template of the class generated in the present invention on (a) pure titanium layer and (b) pure titanium layer
The nano-tube array of generation；
Fig. 3 shows the consistency and elasticity modulus of a vibrating membrane in the embodiment of the present invention with the change curve of compression distance.
Embodiment
The present inventor, by repetition test, is had found in the metal as high frequency diaphragm by in-depth study extensively
Substrate surface generates the oxide of one layer of metal base, can effectively improve the consistency and elasticity modulus of high frequency diaphragm.
With the help of this thinking, the inventors discovered that by advanced multistep anodic oxidation treatment technology, can be in metal base
The metal oxide nanotubes array of surface construction high-sequential, pass through the diameter to nanotube in nano-tube array and length
Regulation and control, the audio and tonequality of vibrating membrane can be effectively improved.Meanwhile by anodized technology, can also be in metal base
The multicoloured compact metal oxide layer of Surface Creation, the oxide layer have better than virgin metal base material consistency and elasticity modulus,
It can be used as high-quality vibrating membrane.The present invention is completed on this basis.
Vibrating membrane
The vibrating membrane of the present invention includes metal base and the gold generated in the metallic substrate surface by anodized
Belong to oxide skin(coating), the metal oxide layer of generation can improve the consistency and elasticity modulus of base metal base material, and significantly improving makes
With the audio and tonequality of the loudspeaker of the vibrating membrane.
Metal oxide layer
The metal oxide layer of the present invention be directly on the surface of metal base by made from anodized, its
In, the metal oxide layer has one or more following characteristics for improving audio and/or tonequality：
(i) metal oxide layer has nano-tube array structure；
(ii) hardness of the metal oxide layer and/or modulus of elasticity are more than the hardness and/or bullet of the metal base
Property modulus.
Nano-tube array structure
The nano-tube array structure of the present invention refers to be arranged with layer of metal oxygen in the surface of metal base, high-sequential
The angle on compound nanotube, the radial direction of these nanotubes and the surface of metal base is 70~90 °.
Anodized
The oxide layer of metal surface autoxidation generation was not only soft but also thin and perishable, therefore through frequently with anodized
Method generate the high anode oxide film of one layer of corrosion-resistant hardness in metal surface.The anodized of the present invention refers to gold
Category base material is placed in corresponding electrolyte as anode, under specified conditions and impressed current effect, is electrolysed, as sun
The metallic substrate surface of pole generates the thin oxide layer of one layer of metal.
The preparation method of vibrating membrane
Present invention also offers the preparation method of vibrating membrane of the present invention.Generally, this method includes：
Metal base is provided；
Metal oxide layer is generated at least one main surface of the metal base, obtains the vibrating membrane, specifically,
A kind of preparation method of preferable vibrating membrane, comprises the following steps：
Surface preparation is carried out in metal base, is successively carried out in alkali wash water and pickle at oil removing and derusting activation
Reason, then cleaned using ultrasonic wave in acetone soln, air-dried after taking-up；
It is configured to the electrolyte aqueous solution containing fluorine ion of anodized；
In the electrolyte aqueous solution containing fluorine ion, using the metal base as anode, to the metal base
Anodized is carried out, so as to have the first metal of nano-tube array structure at least one main Surface Creation of metal base
Oxide skin(coating), used in anodized is metal or graphite cake to electrode；
Sur-face peeling by the nanotube in first metal oxide layer from the metal base, obtain main surface tool
There is the metal base of nano-tube array template；
In described electrolyte aqueous solution, there is the metal base of nano-tube array template as sun using the main surface
Pole, anodized is carried out to the metal base, there is the second metal of nano-tube array structure in the main Surface Creation
Oxide skin(coating), obtains the vibrating membrane, and used in anodized is metal or graphite cake to electrode；
By generation with metal base-vibrating membranes of the second metal oxide Rotating fields with nano-tube array structure
Follow-up ultrasonic wave cleaning treatment is carried out in acetone soln.
It is preferred that the anodic oxidation voltage of above-mentioned anodized is 5V~100V, oxidization time be 20min~
150min, electrolyte temperature are 10 DEG C~100 DEG C.
In addition, in the present invention, the preparation method of another preferable vibrating membrane, comprise the following steps：
Surface preparation is carried out to metal base, successively carried out in alkali wash water and pickle at oil removing and derusting activation
Reason, then cleaned using ultrasonic wave in acetone soln, air-dried after taking-up；
Configure the phosphoric acid electrolyte aqueous solution；
Using the metal base as anode in the electrolyte aqueous solution, anodized is carried out to metal base,
So that in the Surface Creation metal oxide layer of the metal base, the vibrating membrane is obtained, wherein, the metal oxide layer of generation is in
Existing different color.
The above-mentioned vibrating membrane of generation is carried out to follow-up ultrasonic wave cleaning treatment in acetone soln.
Using
The vibrating membrane of the present invention can be used for conventional various electro-acoustic transducer devices, such as loudspeaker, in various sounding
It can be used in electronic and electrical equipment.More preferably, in high pitch and high frequency microphone device, sounding effect is more preferable.
Main advantages of the present invention include：
(a) layer of oxide layer is directly generated by anodized technology in metallic substrate surface, can effectively improved
The consistency and elasticity modulus of vibrating membrane, improve the audio and tonequality of vibrating membrane.
(b) metal oxide layer with nano-tube array structure of the invention is by multistep anodic oxidation treatment technology system
It is standby, it regard the nanotube generated for the first time as template after metallic substrate surface stripping, progress is secondary or multiple generation, generation
Metal oxide nanotubes are not easy to drop under mechanical oscillation, have higher intensity and corrosion resistance, the table as vibrating membrane
Face can make it have more excellent acoustical behavior.
(c) titanium or aluminium and its alloy material have high intensity, excellent corrosion-resistant and mechanical property, pass through advanced multistep
Anodized technology, the nano-tube array of high-sequential, the nanotube can be constructed in titanium or aluminium alloy diaphragm face
Array can also make a significant impact on the audio and tonequality of loudspeaker, by the diameter and length that regulate and control nanotube in nano-tube array
Degree can also improve the audio and tonequality of vibrating membrane, be the vibrating membrane that disclosure satisfy that high pitch and frequency applications demand.
(d) titanium alloy surface is handled by electrochemical anodic oxidation, and can not only be formed on its surface has rich colors
Oxide skin(coating), and the oxide skin(coating) have higher than bulk material consistency and elasticity modulus, loudspeaker can be significantly improved
Audio and tonequality.
Embodiment 1
Vibrating membrane No.1
Vibrating membrane is prepared as metal base using pure titanium below, comprised the following steps：
(1) surface preparation is carried out to pure titanium metal base material, successively cleans 2 in 5~20wt.% sodium hydrate aqueous solutions
~10min, sodium hydroxide wash temperature are 40~150 DEG C.After metal base is cleaned with clear water, it is put into pickle and cleans 2
~10min, pickle proportioning is hydrofluoric acid (10ml)+nitric acid (40ml)+deionized water (300ml).Vibrating membrane after pickling with
Ultrasonic wave cleans in acetone soln afterwards, is air-dried after taking-up.
(2) it is configured to the 3wt.% phosphoric acid electrolyte aqueous solution of electrochemical anodic oxidation.
(3) anodized is carried out to pure titanium metal base material in electrolyte aqueous solution, it is right used in anodized
Electrode is graphite electrode.Anodic oxidation voltage is respectively 20V, 30V and 50V, oxidization time 10min, is electrolysed in oxidizing process
Matter temperature is 20 DEG C.
(4) follow-up ultrasonic wave cleaning treatment is carried out after diaphragm face anodic oxidation to it in acetone soln.As
Vibrating membrane No.1.
Vibrating membrane prepared by the present embodiment 1 as shown in Figure 1, passes through the change of voltage, you can with diaphragm face
The oxide skin(coating) of different colours is formed, the thickness of oxide skin(coating) is about 10~200nm, and the oxide skin(coating) has apparently higher than matrix
Consistency and elasticity modulus, the Frequency Response of loudspeaker can be improved, be effectively improved its tonequality.
Embodiment 2
Vibrating membrane No.2
Vibrating membrane is prepared as metal base using pure titanium below, comprised the following steps：
(1) to pure titanium metal base material carry out surface preparation, first in 5~20wt.% sodium hydrate aqueous solutions cleaning 2~
10min, alkali wash water temperature are 40~150 DEG C.After being cleaned with clear water, 2~10min of cleaning in pickle, pickle proportioning are put into
For hydrofluoric acid (10ml)+nitric acid (40ml)+deionized water (300ml).Pure titanium metal base material after pickling is then in acetone soln
Middle ultrasonic wave cleaning, is air-dried after taking-up.
(2) it is configured to the electrolysis of fluorides liquid of electrochemical anodic oxidation, NH in electrolyte4F contents are 0.25wt.%,
Deionized water content is 2wt.%, and remaining composition is ethylene glycol.
(3) anodized is carried out to pure titanium vibrating diaphragm in electrolyte aqueous solution, it is right used in anodized
Electrode is graphite electrode, and electrolyte temperature is 20 DEG C in oxidizing process.Anodic oxidation is carried out in two steps, first step anodic oxidation electricity
Press as 60V, oxidization time 60min, the nanotube oxide of formation can then be peeled off by mechanical oscillation, formed on matrix
The bowl-shape nano-tube array template of class, as depicted in figure 2.Second step anodic oxidation, it is in the bowl-shape nano-tube array template of class
On continue anodic oxidation, oxidization time 60min, you can prepare length be 20 μm, the titanium oxide nanometer of high-sequential
Pipe array, as shown in accompanying drawing 2b.
(4) follow-up ultrasonic wave cleaning treatment is carried out after diaphragm face anodic oxidation to it in acetone soln.As
Vibrating membrane No.2.
Diaphragm face oxide prepared by the embodiment 2 has unique knot of high-sequential oxide nanotube array
Structure, the structure can substantially significantly affect the audio and acoustical quality of loudspeaker.
Testing example
1. the test data of vibrating membrane No.1 consistency and elasticity modulus.
Vibrating membrane No.1 titanium oxide layer thickness is 100nm, as shown in figure 3, when compression distance is between 0~100nm, is shaken
After dynamic film keeps higher hardness, compression distance to be higher than 100nm, particularly after 150nm, the hardness of vibrating membrane starts quickly
Decline, illustrate the hardness of vibrating membrane titanium oxide layer apparently higher than base material.Meanwhile the modulus of elasticity of vibrating membrane is higher than in compression distance
Also drastically decline (as shown in Figure 3 b) after 100nm.Illustrate that there is obvious height using oxide layer caused by the phosphoric acid electrolyte aqueous solution
In the consistency and elasticity modulus of matrix.
2. pure titanium layer, vibrating membrane No.1 and vibrating membrane No.2 is vibration film production loudspeaker No.1, loudspeaker No.2 and raise
Sound device No.3 tonequality test and appraisal.
Respectively using above-mentioned pure titanium layer, vibrating membrane No.1 and vibrating membrane No.2 as vibration film production loudspeaker No.1, loudspeaker
No.2 and loudspeaker No.3.Below by test loudspeaker No.1, loudspeaker No.2 and loudspeaker No.3 tonequality.
Assessment of acoustics project and scale are set：5 projects, respectively third dimension, location sense, spatial impression, stereovision are set
And thickness sense.Wherein, third dimension is mainly by the spatial impression (Ambience), location sense (sense of direction), stereovision (thickness of sound
Sense) etc. the sense of hearing that is formed, have the sound of these senses of hearing referred to as stereo；Location sense refers to sound source with left and right, upper and lower, front and rear
Sent after different azimuth recording, and recipient receives the sound reset, the sensation that the orientation of sound source in original sound field is reappeared out；
Spatial impression refers to that the primary event sound for lagging direct sound wave and multiple reflections reverberation sound reach two ears from all quarter, and the sense of hearing is judged
Surrounding space size produces material impact, human ear is produced by around the sensation surrounded；Stereovision refers to the high, medium and low frequency of sound
Frequency response is balanced, and high pitch is homophonic abundant, limpid very thin without ear-piercing, and middle pitch is bright to be protruded, and plentiful to enrich without stiff, bass is abundant
And without nasal sound；Thickness sense refers to that bass is sedate strong, and weight thickness does not lack without muddiness, high pitch, and volume is moderate, there is certain brightness, mixes
It is suitable to ring, and distortion is small.
The maximum scale of above-mentioned each project is 9, and projects are with 1 point of scoring unit, corresponding to each scale of projects
The meaning of value is shown in Table 1.
Check problem；Sample and check table are provided to sound expert is commented, it is desirable to comment sound expert to refer to according to form requirement to items
Mark is evaluated.Lateral comparison of the evaluation result carried out just for above-mentioned three kinds of vibrating membranes.
As a result count：It is all comment sound person evaluation result it is effective, ask arithmetic to put down the single item evaluation result for respectively commenting sound person
Average, as a result retain to a decimal, and the arithmetic mean of instantaneous value of each individual event is added and obtains total score, as a result retain to one small
Number.
Table 1 corresponds to the meaning of each scale value of projects
| Score value | Third dimension | Location sense | Spatial impression | Stereovision | Thickness sense |
| 9 | Very well | Very well | It is very strong | It is apparent from | Very well |
| 8 | It is good | It is good | By force | Clearly | It is good |
| 7 | Preferably | Preferably | It is stronger | It is more visible | Preferably |
| 6 | It is slightly good | It is slightly good | It is slightly strong | It is slightly clear | It is slightly good |
| 5 | In | In | In | In | In |
| 4 | It is slightly worse | It is slightly worse | It is slightly weak | It is slightly fuzzy | It is slightly worse |
| 3 | It is poor | It is poor | It is weaker | It is relatively fuzzy | It is poor |
| 2 | Difference | Difference | It is weak | It is fuzzy | Difference |
| 1 | It is very poor | It is very poor | It is very weak | It is very fuzzy | It is very poor |
The Analyses Methods for Sensory Evaluation Results of table 2
| Sample | Third dimension | Location sense | Spatial impression | Stereovision | Thickness sense | It is total |
| Loudspeaker No.1 | 5 | 5 | 5 | 5 | 5 | 5 |
| Loudspeaker No.2 | 6 | 5 | 5 | 6 | 7 | 5 |
| Loudspeaker No.3 | 6 | 7 | 6 | 6 | 5 | 5 |
The third dimension of vibrating membrane after phosphoric acid oxidation as shown in Table 2, thickness sense and stereovision are better than untreated vibration
Film, and the third dimension of the vibrating membrane of high-sequential nano-tube array is prepared, location sense, spatial impression and stereovision will be substantially better than not
The vibrating membrane of processing.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. a kind of vibrating membrane, it is characterised in that the vibrating membrane includes metal base and positioned at least one master of the base material
Metal oxide layer on surface, wherein, the metal oxide layer has one or more improvement acoustic characteristics and/or tonequality
Following characteristics：
(i) metal oxide layer has orderly nano-tube array structure；
(ii) hardness of the metal oxide layer and/or modulus of elasticity are more than the hardness and/or springform of the metal base
Amount；
And the metal oxide layer is generated by anodized.
2. vibrating membrane according to claim 1, it is characterised in that the substrate metal includes the metal being selected from the group：It is pure
Titanium, titanium alloy, fine aluminium, aluminium alloy, or its combination.
3. vibrating membrane according to claim 1, it is characterised in that the metal oxide with nano-tube array structure
Layer includes titanium oxide and/or aluminum oxide.
4. vibrating membrane according to claim 3, it is characterised in that the average length of the nanotube is 1 μm~50 μm；
And/or the average diameter of the nanotube is 20~150nm.
5. a kind of loudspeaker, it is characterised in that the loudspeaker includes the vibrating membrane described in any one of Claims 1-4.
6. a kind of preparation method of vibrating membrane as claimed in claim 1, it is characterised in that comprise the following steps：
(a) metal base is provided；
(b) first metal oxide of the generation with nano-tube array structure at least one main surface of the metal base
Layer；
(c) nanotube of first metal oxide layer is peeled off, obtaining main surface has nano-tube array structure template
Metal base；
(d) second with nano-tube array structure is generated on main surface of the metal base with the nano-tube array template
Metal oxide layer, obtain the vibrating membrane.
7. the preparation method of vibrating membrane according to claim 6, it is characterised in that the step (b) includes：
Configure the electrolyte aqueous solution containing fluorine ion；
In the electrolyte aqueous solution containing fluorine ion, using the metal base as anode, the metal base is carried out
Anodized, so as to which generation has the first of nano-tube array structure at least one main surface of the metal base
Metal oxide layer；
And/or the step (c) includes：
The nanotube in first metal oxide layer is peeled off by mechanical oscillation, in the main table of the metal base
Nano-tube array template is generated on face, obtaining main surface has the metal base of nano-tube array structure template；
And/or the step (d) includes：
In described fluorine ion electrolyte aqueous solution, there is the metal base of the nano-tube array template as sun using main surface
Pole, anodized is carried out to the metal base, there is the second metal of nano-tube array structure in the main Surface Creation
Oxide skin(coating), obtain the vibrating membrane.
8. preparation method according to claim 7, it is characterised in that the electrolyte aqueous solution containing fluorine ion includes
The fluoride being selected from the group：Ammonium fluoride, potassium fluoride, sodium fluoride or its combination；And/or
The electrolyte aqueous solution containing fluorine ion includes the additive being selected from the group：Deionized water, glycerine, ethylene glycol,
Methanol or its combination.
9. preparation method according to claim 8, it is characterised in that the fluoride is ammonium fluoride, it is described containing fluorine from
The content of ammonium fluoride is 0.01~2.5wt.% in the electrolyte aqueous solution of son.
10. a kind of preparation method of vibrating membrane as claimed in claim 1, it is characterised in that comprise the following steps：
(a1) metal base is provided；
(b1) in the phosphoric acid electrolyte aqueous solution, using the metal base as anode, anodic oxidation is carried out to the metal base
Processing, generates metal oxide layer at least one main surface of the metal base, obtains the vibrating membrane.
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| WO2019047082A1 (en) * | 2017-09-06 | 2019-03-14 | 深圳市同富达电子科技有限公司 | Method for forming aluminum surface selenium treated nano coating for improving low frequency extension of earphone |
| CN107904556A (en) * | 2017-10-23 | 2018-04-13 | 宁波大红鹰学院 | One kind prepares patterning function film method based on templated deposition |
| CN113132887B (en) * | 2021-04-20 | 2022-07-22 | 东莞舒铂迈特精工实业有限公司 | Metal ring processing technology of vibrating diaphragm assembly |
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| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
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| KR100649092B1 (en) * | 2005-11-02 | 2006-11-27 | 한국과학기술연구원 | Metal oxide supercapacitor having metal oxide electrode coated onto the titanium dioxide ultrafine and its fabrication method |
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| CN1159726A (en) * | 1995-12-08 | 1997-09-17 | 日本先锋公司 | Vibration membrane for loudspeaker |
| CN101288336A (en) * | 2005-10-14 | 2008-10-15 | Kh化学有限公司 | Acoustic diaphragm and speakers having the same |
| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
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