CN106744992A - A kind of molecular sieve hollow ball for strengthening low frequency performance and preparation method thereof - Google Patents
A kind of molecular sieve hollow ball for strengthening low frequency performance and preparation method thereof Download PDFInfo
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- CN106744992A CN106744992A CN201710062532.1A CN201710062532A CN106744992A CN 106744992 A CN106744992 A CN 106744992A CN 201710062532 A CN201710062532 A CN 201710062532A CN 106744992 A CN106744992 A CN 106744992A
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- molecular sieve
- hollow ball
- sieve hollow
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- low frequency
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention proposes a kind of molecular sieve hollow ball and preparation method thereof, including SiO2, oxide MxOy；The molecular sieve hollow ball Si/M atomic ratios are more than 50, diameter between 10 microns 2 millimeters；Wherein M is one or more in A1, Fe, V, Zr, P, B.Molecular sieve hollow ball proposed by the invention, it is adaptable to electro-acoustic element, as sound-absorbing material, can cause that electro-acoustic element system shows more preferable low frequency performance：Overall f0Reduce, the sound pressure level of low frequency part increases.
Description
【Technical field】
The present invention relates to a kind of electro-acoustic element sound-absorbing material, refer specifically to it is a kind of can strengthen electro-acoustic element low frequency performance point
Son sieve hollow ball and preparation method thereof.
【Background technology】
In electro-acoustic element device, porous material is added in the box cavitys at its back, can played equivalent to increase chamber
The effect of body volume, so that electro-acoustic element system shows more preferable low frequency performance：Overall f0Reduce, low frequency portion
The sound pressure level for dividing increases.
The low frequency used in existing patent improves the active charcoal of material, zeolite, molecular sieve, MgO, Al2O3、SiO2Deng；It is logical
Often, these materials are all powdered, or are manufactured into by way of shaping during larger particle uses product；Such as patent
In CN103098490A, from the zeolite particles of 0.1-10 micron grain sizes, add binding agent be shaped to 0.2-0.9 millimeters
Grain；This occupation mode has been damaged due to the presence for having adhesive, the low frequency performance to electro-acoustic element.Therefore, it is necessary to carry
Going out a kind of new electro-acoustic element low frequency performance improves material and structure.
【The content of the invention】
The present invention optimizes research for for improving the molecular sieve structure of electro-acoustic element low frequency performance, so as to provide one
Plant molecular sieve hollow ball.
To achieve the above object, the present invention proposes following scheme：
A kind of molecular sieve hollow ball, including SiO2, oxide MxOy；The molecular sieve hollow ball Si/M atomic ratios more than 50,
Diameter is between 10 microns -2 millimeters；Wherein M is one or more in Al, Fe, V, Zr, P, B.
Preferably, the structure type of the molecular sieve hollow ball includes one or more in MFI, MEL, MRE, β, FER.
Preferably, UNICOM duct is included between the surfaces externally and internally of the molecular sieve hollow ball.
Preferably, the Si/M atomic ratios are between 60-200.
The present invention also proposes a kind of sound-absorbing material, including molecular sieve hollow ball proposed by the invention.
The present invention also proposes a kind of preparation method of molecular sieve hollow ball, comprises the following steps：
The silicon source of proper ratio, alkali, template, M sources, water is taken to be synthesized.
Preferably, the silicon source includes silica, tetraethyl orthosilicate, sodium metasilicate or Ludox.
Preferably, the alkali includes NaOH, potassium hydroxide or ammoniacal liquor.
Preferably, the template includes one or more in organic amine, organic amine salt or organic base.
The present invention also proposes a kind of electro-acoustic element, including molecular sieve hollow ball or the sound absorption that is made up of molecular sieve hollow ball
Material.
The beneficial effects of the invention are as follows：By adding proposed by the invention dividing in the box cavitys at electro-acoustic element back
Son sieve hollow ball or the sound-absorbing material being made up of the molecular sieve hollow ball, can play equivalent to the effect for increasing cavity volume
Really, so that electro-acoustic element system shows more preferable low frequency performance：Overall f0Reduce, the sound pressure level of low frequency part
Increase.
【Brief description of the drawings】
Fig. 1 is the SEM photograph of the MFI molecular sieve hollow balls of the embodiment of the present invention 1.
Fig. 2 is the hollow ball surface linked hole SEM photograph of MFI molecular sieves of the embodiment of the present invention 1.
Fig. 3 is the MFI molecular sieve hollow balls XRD test collection of illustrative plates of the embodiment of the present invention 1.
Fig. 4 is the SEM photograph of the MRE molecular sieve hollow balls of the embodiment of the present invention 3.
Fig. 5 is the XRD test collection of illustrative plates of the MRE molecular sieve hollow balls of the embodiment of the present invention 3.
Fig. 6 is the frequency response curve of electro-acoustic element of the present invention.
【Specific embodiment】
With reference to Fig. 1 to Fig. 6, the present invention is described in detail.
Molecular sieve (also known as synthetic zeolite) is a kind of many microporous crystals of alumino-silicate.It is by silica, aluminum-oxygen tetrahedron group
Into basic skeleton structure, metal cation (such as Na+, K+, Ca2+, Li+ etc.) is there is outside skeleton, it is many in crystal to balance
Remaining negative electrical charge.Molecular sieve can be divided into kind more than 200, such as FER, FAU, BEA, MFI by its framework types.
Molecular sieve applied in the collecting cavity of electro-acoustic element as sound-absorbing porous material, being capable of effective boost device
Low frequency audio.
Generally, molecular sieve is being applied in electro-acoustic element, it is necessary to be molded after adding adhesive, and adhesive makes
With can have a negative impact to the performance of electro-acoustic element；The present invention is direct by preparing the molecular sieve with hollow spheres structure
Used as the sound-absorbing material of electro-acoustic element.The diameter of molecular sieve hollow ball of the invention between 10 microns -2 millimeters, and
And with the presence of substantial amounts of UNICOM duct between the surfaces externally and internally of this molecular sieve hollow ball, air can touch ball interior surface, increase
Big contact area, helps further to lift the low frequency performance of electro-acoustic element.
Molecular sieve hollow ball of the invention can be MFI, MEL, MRE, β, FER equimolecular sieve structure type；In molecular sieve
10 microns -2 millimeters of the diameter of empty ball, 10 microns of ＜, packaging difficulty is big when using, and accumulation can closely cause internal gas flow communication
Resistance it is big, be unfavorable for performance；2 millimeters of ＞ is not easy to prepare hollow structure, and the intensity of hollow ball is poor, broken.
Molecular sieve hollow ball of the invention is main by SiO2Composition, additionally can simultaneously contain other oxide MsxOy(M
Can be in Al, Fe, Ti, V, Ge, Zr, P, B etc. one or more), and Si/M atomic ratios are more than 50；＜ 50 can cause water absorption rate
It is higher, block duct, penalty.
For preparation method, molecular sieve hollow ball of the invention can by silicon source (silica, tetraethyl orthosilicate,
Sodium metasilicate, Ludox etc.), alkali (NaOH, potassium hydroxide, ammoniacal liquor), template (quaternary ammonium salt, quaternary ammonium base, hexamethylene diamine, butylamine,
In the organic amines such as propylamine, isopropylamine, ethylenediamine or organic base one or more), the M sources (oxide in molecular sieve
Calmly), the synthesis such as water is obtained.
Embodiment 1：
The molecular sieve hollow ball of MFI structure, the preparation method of the present embodiment is as follows：
Synthesized from suitable silicon source, alkali, template, source of iron and water, wherein, the silicon source in the present embodiment can be
Silica, tetraethyl orthosilicate, sodium metasilicate, Ludox etc.；Alkali is for example including NaOH, potassium hydroxide, ammoniacal liquor etc.；Template
Agent, can be the one kind in the organic amines such as quaternary ammonium salt, quaternary ammonium base, hexamethylene diamine, butylamine, propylamine, isopropylamine, ethylenediamine or organic base
Or it is various；Source of iron can be iron oxide, ferric nitrate, ferric sulfate, iron chloride, iron hydroxide etc..
The present embodiment synthesizes Si/Fe than the MFI structure molecular sieve hollow ball for 40-80 μm of 60, diameter, its pattern referring to
Fig. 1, it can be seen that ball has obvious hollow structure after ball is crushed.Referring to Fig. 2, ball surface is with the presence of substantial amounts of through hole；This leads to
Hole allows that air touches ball interior surface, increase effectively contact area；Referring to Fig. 3, XRD display molecular sieve hollow balls
Belong to MFI structure molecular sieve.
This molecular sieve hollow ball is filled into the test fixture of 1cc cavitys, its acoustic response result is tested as shown in table 1
Table 1
Embodiment 2
Same as Example 1, the present embodiment is also the molecular sieve hollow ball for preparing MFI structure, preparation method and embodiment 1
Identical, difference is：Source metal uses silicon source, such as aluminum oxide, aluminum nitrate, aluminum sulfate, aluminium hydroxide etc.；Synthesis Si/
Al is than the MFI structure molecular sieve hollow ball for 100, diameter 200-300 um.
This molecular sieve hollow ball is filled into the test fixture of 1cc cavitys, test result is as shown in table 2：
Table 2
Embodiment 3
The molecular sieve hollow ball of MRE structures, preparation method is as follows：
With silicon source, such as silica, tetraethyl orthosilicate, sodium metasilicate, Ludox etc., alkali, such as NaOH, hydroxide
Potassium, ammoniacal liquor etc., the organic amine such as template, such as quaternary ammonium salt, quaternary ammonium base, hexamethylene diamine, butylamine, propylamine, isopropylamine, ethylenediamine or have
One or more in machine alkali, Al sources, such as aluminum oxide, aluminum nitrate, aluminum sulfate, aluminium hydroxide etc., and be hydrated into Si/Al ratio and be
80th, the MRE structure molecular screen hollow balls of diameter 40-80um, shown in its pattern and XRD spectrum Fig. 4 and Fig. 5.Can after ball is crushed
With find out ball have obvious shell structure, referring to Fig. 4；XRD displays molecular sieve hollow ball belongs to MRE structure molecular screens, referring to Fig. 5.
This molecular sieve hollow ball is filled into the test fixture of 1cc cavitys, test result is as listed in table 3：
Table 3
Test result shows：Can be played equivalent to increasing after adding this material in the box cavitys at electro-acoustic element back
Plus the effect of cavity volume, so that electro-acoustic element system shows more preferable low frequency performance：Overall f0Reduce, it is low
The sound pressure level of frequency part increases.
Embodiment 4
The molecular sieve hollow ball of MEL structures, preparation method is as follows：
With silicon source, such as silica, tetraethyl orthosilicate, sodium metasilicate, Ludox etc., alkali, such as NaOH, hydroxide
Potassium, ammoniacal liquor etc., the organic amine such as template, such as quaternary ammonium salt, quaternary ammonium base, hexamethylene diamine, butylamine, propylamine, isopropylamine, ethylenediamine or have
One or more in machine alkali；Silicon source, such as aluminum oxide, aluminum nitrate, aluminum sulfate, aluminium hydroxide etc., and be hydrated into Si/Al ratio and be
200th, the MEL structure molecular screen hollow balls of diameter 300-500um.
This molecular sieve hollow ball is filled into the test fixture of 1cc cavitys, test result is as shown in table 4：
Table 4
In various embodiments above, F0Value refers to electro-acoustic element low-frequency range impedance value in free found field and reaches maximum
When corresponding frequency, Q values then reflect electro-acoustic element in F0The damping state of neighbouring vibrational system, is to determine electro-acoustic element
The important parameter of low frequency characteristic.
Referring to Fig. 6, A lines represent test curve, the B lines tables of no added molecular sieve of the present invention or sound-absorbing material in figure
Show the test curve for being added with molecular sieve hollow ball of the present invention.Test result shows：Add in the box cavitys at electro-acoustic element back
Plus can be played after this material equivalent to the effect for increasing cavity volume, so that electro-acoustic element system shows more
Good low frequency performance：Overall f0Reduce, the sound pressure level of low frequency part increases.
Above-described is only embodiments of the present invention, it should be noted here that for one of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
Enclose.
Claims (10)
1. a kind of molecular sieve hollow ball, it is characterised in that：Including SiO2, oxide MxOy；The molecular sieve hollow ball Si/M atoms
Than more than 50, diameter between 10 microns -2 millimeters；Wherein M is one or more in Al, Fe, V, Zr, P, B.
2. molecular sieve hollow ball according to claim 1, it is characterised in that：The structure type bag of the molecular sieve hollow ball
Include one or more in MFI, MEL, MRE, β, FER.
3. molecular sieve hollow ball according to claim 1, it is characterised in that：Between the surfaces externally and internally of the molecular sieve hollow ball
Including UNICOM duct.
4. molecular sieve hollow ball according to claim 1, it is characterised in that：The Si/M atomic ratios between 60-200 it
Between.
5. the molecular sieve hollow ball described in a kind of sound-absorbing material, including claim any one of 1-4.
6. the preparation method of the molecular sieve hollow ball described in claim 1, comprises the following steps：
Silicon source, alkali, template, M sources and the water for taking proper ratio are synthesized.
7. the preparation method of molecular sieve hollow ball according to claim 5, it is characterised in that：The silicon source includes titanium dioxide
Silicon, tetraethyl orthosilicate, sodium metasilicate or Ludox.
8. the preparation method of molecular sieve hollow ball according to claim 5, it is characterised in that：The alkali includes hydroxide
Sodium, potassium hydroxide or ammoniacal liquor.
9. the preparation method of molecular sieve hollow ball according to claim 5, it is characterised in that：The template includes organic
One or more in amine, organic amine salt or organic base.
10. described in the molecular sieve hollow ball or claim 5 described in a kind of electro-acoustic element, including claim any one of 1-4
Sound-absorbing material.
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| CN201710062532.1A CN106744992B (en) | 2017-01-23 | 2017-01-23 | A kind of molecular sieve hollow ball and preparation method thereof for enhancing low frequency performance |
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| CN201710062532.1A CN106744992B (en) | 2017-01-23 | 2017-01-23 | A kind of molecular sieve hollow ball and preparation method thereof for enhancing low frequency performance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110614121A (en) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve, preparation method and application thereof |
| CN110615444A (en) * | 2018-06-20 | 2019-12-27 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve, and preparation method and application thereof |
| US11140475B2 (en) * | 2018-07-28 | 2021-10-05 | Aac Acoustic Technologies (Shenzhen) Co., Ltd. | Sound absorbing material, method for process same and speaker using same |
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| US11140475B2 (en) * | 2018-07-28 | 2021-10-05 | Aac Acoustic Technologies (Shenzhen) Co., Ltd. | Sound absorbing material, method for process same and speaker using same |
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| CN106744992B (en) | 2019-08-27 |
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Granted publication date: 20190827 Termination date: 20220123 |