CN111479209B - Loudspeaker diaphragm composite material - Google Patents
Loudspeaker diaphragm composite material Download PDFInfo
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- CN111479209B CN111479209B CN202010182954.4A CN202010182954A CN111479209B CN 111479209 B CN111479209 B CN 111479209B CN 202010182954 A CN202010182954 A CN 202010182954A CN 111479209 B CN111479209 B CN 111479209B
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R31/00—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor
- H04R31/003—Apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor for diaphragms or their outer suspension
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2231/00—Details of apparatus or processes specially adapted for the manufacture of transducers or diaphragms therefor covered by H04R31/00, not provided for in its subgroups
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/025—Diaphragms comprising polymeric materials
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/027—Diaphragms comprising metallic materials
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R2307/00—Details of diaphragms or cones for electromechanical transducers, their suspension or their manufacture covered by H04R7/00 or H04R31/003, not provided for in any of its subgroups
- H04R2307/029—Diaphragms comprising fibres
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Signal Processing (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Abstract
The invention provides a loudspeaker diaphragm composite material which is formed by compounding a modified cellulose polyester composite film, a composite structure adhesive layer and a metal composite film layer. This loudspeaker diaphragm combined material adopts modified cellulose polyester composite film bonding metal composite film's composite construction, not only can effectively strengthen this loudspeaker diaphragm combined material's rigidity through metal composite film, the ability that the biggest vibration of reinforcing loudspeaker diaphragm combined material bore, higher elasticity has been remain through modified cellulose polyester composite film simultaneously, and can take place subtle co-vibration between modified cellulose polyester composite film (plastics material) and the metal composite film layer (metal material) among the vibration process, make this loudspeaker diaphragm combined material possess good transient state, sensitivity and frequency response, the tone quality is effectual.
Description
Technical Field
The invention relates to a composite material, in particular to a loudspeaker diaphragm composite material.
Background
The loudspeaker unit mainly comprises a vibration sounding part (a vibrating diaphragm, a voice coil, a framework and a dust cover), a supporting reset centering part (a folded ring or a suspended edge, a centering support sheet or an elastic wave) and a magnetic field providing part (a magnet, a magnetic conduction column and an upper magnetic conduction plate and a lower magnetic conduction plate). When an alternating audio voltage signal passes through a voice coil of the loudspeaker, the voice coil is driven by ampere force under the action of a magnetic field, the voice coil reciprocates at the balance position of the voice coil, and the vibrating diaphragm moves together with the voice coil; the vibration of the vibrating diaphragm can push the vibration of the surrounding air medium, and the radiation acoustic resistance is formed at the mechanical end; the energy is transferred through the air medium, so that the electro-mechanical-acoustic conversion is realized. According to the calculation formula of the ampere force, the amplitude of the audio alternating voltage signal is positively correlated with the amplitude of the reciprocating motion of the voice coil, and the larger the amplitude of the music signal is, the louder the sound emitted by the loudspeaker is; while the frequency of the audio voltage signal affects the pitch of the sound.
The loudspeaker diaphragm is the main component of the loudspeaker, and the loudspeaker (especially the midbass loudspeaker) generates sound by converting electromagnetic force to the diaphragm tightly connected with the loudspeaker diaphragm through a voice coil at the center of the diaphragm to form mechanical force so as to complete the electric-force-sound conversion. The diaphragm is the central mechanical part and the most important part in the electro-acoustic-electro-acoustic conversion process, and can affect the acoustic performance of the loudspeaker. The performance of the diaphragm depends on the geometry, material, and processing technology of the diaphragm, and the basic parameters affecting the acoustic performance of the diaphragm material include mass, density, rigidity, internal loss (internal damping), and the like.
The existing loudspeaker diaphragm composite material generally adopts a plastic diaphragm as follows: PET/PEN/PEI/PI/LCP/PEEK/PC/PPS/PAR and the like; other types of diaphragms such as: wood diaphragm/biological diaphragm/paper diaphragm, etc. The vibrating membranes made of different materials have different elastic moduli, internal damping, poisson ratios, thicknesses, densities and the like, and the differences directly influence the quality factor Q value (damping coefficient) of the loudspeaker to cause different qualities of the earphone unit. Therefore, it is a matter of current industry to advance to develop and test loudspeaker diaphragm composite materials of different materials, especially to develop loudspeaker diaphragm composite materials of composite materials to obtain different tone quality feelings.
Disclosure of Invention
The invention provides a loudspeaker diaphragm composite material, which adopts a structure that a specially-made composite structural adhesive is used for compounding a modified cellulose polyester composite film and a metal composite film, has high rigidity and high elasticity, has good transient state, sensitivity and frequency response, and has good sound quality effect.
In order to achieve the above technical solution, the present invention provides a loudspeaker diaphragm composite material, including:
a modified cellulose polyester composite film;
coating the composite structure adhesive layer at the bottom of the modified cellulose polyester composite film;
the metal composite film layer is adhered to the bottom of the composite structure adhesive layer and is prepared by the following method:
s31, cutting the monocrystalline silicon piece into squares with the size of 20mm multiplied by 20mm, putting the squares into an ultrasonic cleaning instrument for ultrasonic cleaning for 20min, and cutting the copper piece with the thickness of 0.01mm into copper pieces with the specification of 500mm multiplied by 500mm for standby;
s32, mounting the CrSi target in a magnetron sputtering coating machine, and adjusting the distance between the CrSi target and the substrate to a proper position; taking out the basal disc, fixing the cut copper sheet on the basal disc, then placing the monocrystalline silicon wafer above the basal copper sheet, installing the basal disc, and closing the vacuum chamber;
s33, turning on a power supply and a circulating water system of the magnetron sputtering coating machine, pre-pumping to about 15Pa by using a mechanical pump, turning on a molecular pump to a high vacuum of 1.5 multiplied by 10-3Pa; then high-purity argon is introduced, the argon flow is set to be 45sccm, and a stop valve is adjusted to stabilize the air pressure in the vacuum chamber at 7 x 10-1Pa；
S34, turning on a direct current power supply, adjusting the sputtering current to 0.5A, and pre-sputtering for 2 min; and then opening a base plate rotating button, setting the rotating speed of the base plate to be 15r/min, opening a target material baffle, carrying out magnetron sputtering deposition, controlling the magnetron sputtering deposition time to be 1h, and cooling for 30min to obtain the Cu-CrSi metal composite film layer.
Preferably, the modified cellulose polyester composite film is prepared by the following method:
s11, weighing 100g of oven-dried needle leaf pulp, adding deionized water, stirring at a high speed to prepare 0.5% pulp, then adding 2g of TEMPO and 12g of NaBr, continuously stirring for 30min, then adding 6g of NaClO, continuously stirring for 30min, and then gradually adding 0.5mol/L NaOH standard solution to adjust the pH to 10 to finish the reaction;
s12, adding 6ml of absolute ethyl alcohol to terminate the reaction, filtering and washing to obtain oxidized wet pulp, adding a proper amount of deionized water to adjust the pulp concentration to 1%, and carrying out high-pressure homogenization treatment for 4 times to obtain a TEMPO oxidized cellulose solution;
s13, placing the TEMPO oxidized cellulose solution prepared in the step S12 into a sand core funnel, performing suction filtration through a connected vacuum pump to obtain wet cellulose powder, taking out the wet cellulose powder, and drying the wet cellulose powder in an oven at 50 ℃ for 24 hours to obtain modified cellulose powder;
s14, weighing 100g of acrylic resin powder and 10g of the cellulose powder prepared in the step S13, mixing and crushing for 5min by a high-speed crusher, then melting and extruding the mixed powder material into a wire shape by a double-screw extruder, and finally cutting into particles by a cold granulator;
s15, adding the particles obtained in the step S14 into a biaxial stretching machine, and preheating, melting, stretching, shaping and cooling the particles through the biaxial stretching machine to obtain the modified cellulose polyester composite film.
Preferably, the composite structure glue layer comprises the following components in percentage by mass: 60-70% of copper powder, 10-20% of polycaprolactone diol, 10-20% of p-phenylene diisocyanate, 0.5-1% of sealing agent diethyl malonate, 1-3% of cross-linking agent pentaerythritol, 0.5-1% of curing agent polythiol, 1-5% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 1-5% of ethylenediamine.
Particularly preferably, the composite structure glue layer comprises the following components in percentage by mass: 65% of copper powder, 12% of polycaprolactone diol, 15% of p-phenylene diisocyanate, 0.8% of sealing agent diethyl malonate, 1.5% of cross-linking agent pentaerythritol, 0.9% of curing agent polythiol, 2% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 3% of ethylenediamine.
Preferably, the composite structural adhesive layer is prepared by the following method:
s21, pouring accurately weighed copper powder into 0.5mol/L diluted hydrochloric acid solution, stirring for 30min for surface treatment, washing with absolute ethyl alcohol solution for a plurality of times, and then drying in vacuum; then adding the treated copper powder into 1.2mol/L silane coupling agent solution, stirring for 20min to enable the copper powder to fully react, washing the copper powder for a plurality of times by using absolute ethyl alcohol solution after suction filtration, then carrying out suction filtration, and taking out the copper powder for later use after vacuum drying;
s22, adding polycaprolactone diol into a vacuum dehydration box, controlling the temperature at 100 ℃ for vacuum dehydration for 2 hours, then adding metered p-phenylene diisocyanate, maintaining the system at 80 ℃ for reaction for 3 hours to obtain a polyurethane prepolymer, then adding a chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt, ethylenediamine and a sealing agent diethyl malonate for continuous reaction for 2 hours, then adding a cross-linking agent pentaerythritol and a curing agent polythiol for continuous reaction for 2 hours to obtain a conductive composite structural adhesive base material;
s23, mixing the copper powder subjected to surface treatment in the step S21 with the conductive composite structural adhesive base material prepared in the step S22, defoaming in vacuum, and casting and molding at the temperature of 90 ℃ to prepare the high-polymerization polyurethane conductive composite structural adhesive;
s24, uniformly coating the polyurethane conductive composite structural adhesive prepared in the step S23 on the bottom of the modified cellulose polyester composite film by using a glue spreader to form a composite structural adhesive layer.
Preferably, the thickness of the modified cellulose polyester composite film is 5-10 μm.
Preferably, the thickness of the composite structure glue layer is 2-5 μm, the thickness of the composite structure glue layer is not too small, otherwise, the adhesive force between the modified cellulose polyester composite film and the metal composite film layer is reduced, a gap is easily generated between the modified cellulose polyester composite film and the metal composite film layer in the vibration process, and the tone quality is seriously affected. The thickness of composite construction glue film should not too big yet, and the whole thickness of vibrating diaphragm is big more, and sensitivity and frequency response are poor more, consequently under the ability that the biggest vibration bore, the holistic thickness of vibrating diaphragm is thinner, and sensitivity and frequency response performance are better.
Preferably, the thickness of the metal composite film layer is 10-15 μm, and the thinner the whole thickness of the vibrating diaphragm is, the better the performance of transient state, sensitivity, frequency response and the like, so the thickness of the modified cellulose polyester composite film and the metal composite film layer is not too large or too small, and the too large thickness of the modified cellulose polyester composite film and the metal composite film layer can deteriorate the performance of transient state, sensitivity, frequency response and the like and has poor sound quality effect; experiments prove that when the modified cellulose polyester composite film with the thickness of 5-10 mu m and the metal composite film layer with the thickness of 10-15 mu m are compounded, good performances such as transient state, sensitivity and frequency response can be obtained on the premise of higher maximum vibration bearing capacity.
The invention has the following beneficial effects:
1) this loudspeaker diaphragm combined material adopts modified cellulose polyester composite film bonding metal composite film's composite construction, not only can effectively strengthen this loudspeaker diaphragm combined material's rigidity through metal composite film, the ability that the biggest vibration of reinforcing loudspeaker diaphragm combined material bore, higher elasticity has been remain through modified cellulose polyester composite film simultaneously, and can take place subtle co-vibration between modified cellulose polyester composite film (plastics material) and the metal composite film layer (metal material) among the vibration process, make this loudspeaker diaphragm combined material possess good transient state, sensitivity and frequency response, the tone quality is effectual.
2) This loudspeaker diaphragm combined material adopts self-made modified cellulose polyester composite film, compares traditional polyester film and has better elastic modulus, littleer internal damping, and tone quality is effectual.
3) This loudspeaker diaphragm combined material adopts self-control electrically conductive composite structure to glue, not only can improve the adhesion stress between modified cellulose polyester composite film and the metal composite film layer, compares traditional gluing agent moreover, has better sound conduction effect.
4) This loudspeaker diaphragm combined material adopts the compound thin layer of self-control metal, compares traditional copper foil material, and frequency bandwidth is bigger, and sensitivity is higher, and the distortion is little, and tone quality is effectual.
Drawings
FIG. 1 is a schematic view of the layered structure of the present invention.
In the figure: 1. a modified cellulose polyester composite film; 2. a composite structural adhesive layer; 3. a metal composite film layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
Example 1: a loudspeaker diaphragm composite material.
Referring to fig. 1, a loudspeaker diaphragm composite material includes:
the modified cellulose polyester composite film 1 is prepared by the following steps:
s11, weighing 100g of oven-dried needle leaf pulp, adding deionized water, stirring at a high speed to prepare 0.5% pulp, then adding 2g of TEMPO (2,2,6, 6-tetramethylpiperidine oxide) and 12g of NaBr, continuously stirring for 30min, then adding 6g of NaClO, continuously stirring for 30min, and then gradually adding 0.5mol/L of NaOH standard solution to adjust the pH to 10 to finish the reaction;
s12, adding 6ml of absolute ethyl alcohol to terminate the reaction, filtering and washing to obtain oxidized wet pulp, adding a proper amount of deionized water to adjust the pulp concentration to 1%, and carrying out high-pressure homogenization treatment for 4 times to obtain a TEMPO oxidized cellulose solution;
s13, placing the TEMPO oxidized cellulose solution prepared in the step S12 into a sand core funnel, performing suction filtration through a connected vacuum pump to obtain wet cellulose powder, taking out the wet cellulose powder, and drying the wet cellulose powder in an oven at 50 ℃ for 24 hours to obtain modified cellulose powder;
s14, weighing 100g of acrylic resin powder and 10g of the cellulose powder prepared in the step S13, mixing and crushing for 5min by a high-speed crusher, then melting and extruding the mixed powder material into a wire shape by a double-screw extruder, and finally cutting into particles by a cold granulator;
s15, adding the particles obtained in the step S14 into a biaxial stretching machine, preheating, melting, stretching, shaping and cooling the particles through the biaxial stretching machine to obtain a modified cellulose polyester composite film, and controlling the thickness of the modified cellulose polyester composite film to be 8 microns;
the composite structure glue layer 2 is coated on the bottom of the modified cellulose polyester composite film 1, and the composite structure glue layer 2 comprises the following components in percentage by mass: 65% of copper powder, 12% of polycaprolactone diol, 15% of p-phenylene diisocyanate, 0.8% of sealing agent diethyl malonate, 1.5% of cross-linking agent pentaerythritol, 0.9% of curing agent polythiol, 2% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 3% of ethylenediamine, and is prepared by the following method:
s21, pouring accurately weighed copper powder into 0.5mol/L diluted hydrochloric acid solution, stirring for 30min for surface treatment, washing with absolute ethyl alcohol solution for a plurality of times, and then drying in vacuum; then adding the treated copper powder into 1.2mol/L silane coupling agent solution, stirring for 20min to enable the copper powder to fully react, washing the copper powder for a plurality of times by using absolute ethyl alcohol solution after suction filtration, then carrying out suction filtration, and taking out the copper powder for later use after vacuum drying;
s22, adding polycaprolactone diol into a vacuum dehydration box, controlling the temperature at 100 ℃ for vacuum dehydration for 2 hours, adding metered p-phenylene diisocyanate, maintaining the system at 80 ℃ for reaction for 3 hours to obtain a polyurethane prepolymer, adding a chain extender N- (2-aminoethyl) -2-aminoethane sodium sulfonate, ethylenediamine and a sealing agent diethyl malonate for continuous reaction for 2 hours, adding a cross-linking agent pentaerythritol and a curing agent polythiol for continuous reaction for 2 hours to obtain a conductive composite structural adhesive base material;
s23, mixing the copper powder subjected to surface treatment in the step S21 with the conductive composite structural adhesive base material prepared in the step S22, defoaming in vacuum, and casting and molding at the temperature of 90 ℃ to prepare the high-polymerization polyurethane conductive composite structural adhesive;
s24, uniformly coating the polyurethane conductive composite structural adhesive prepared in the step S23 on the bottom of the modified cellulose polyester composite film by using a glue spreader to form a composite structural adhesive layer, wherein the thickness of the composite structural adhesive layer is controlled to be 4 micrometers;
the metal composite film layer 3 is adhered to the bottom of the composite structure glue layer 2, and the metal composite film layer 3 is prepared by the following method:
s31, cutting the monocrystalline silicon piece into squares with the size of 20mm multiplied by 20mm, putting the squares into an ultrasonic cleaning instrument for ultrasonic cleaning for 20min, and cutting the copper piece with the thickness of 0.01mm into copper pieces with the specification of 500mm multiplied by 500mm for standby;
s32, mounting the CrSi target in a magnetron sputtering coating machine, and adjusting the distance between the CrSi target and the substrate to a proper position; taking out the basal disc, fixing the cut copper sheet on the basal disc, then placing the monocrystalline silicon wafer above the basal copper sheet, installing the basal disc, and closing the vacuum chamber;
s33, turning on a power supply and a circulating water system of the magnetron sputtering coating machine, pre-pumping to about 15Pa by using a mechanical pump, turning on a molecular pump to a high vacuum of 1.5 multiplied by 10-3Pa; then high-purity argon is introduced, the argon flow is set to be 45sccm,the pressure in the vacuum chamber is stabilized at 7 x 10 by adjusting the stop valve-1Pa；
S34, turning on a direct current power supply, adjusting the sputtering current to 0.5A, and pre-sputtering for 2 min; and then opening a base plate rotating button, setting the rotating speed of the base plate to be 15r/min, opening a target material baffle, carrying out magnetron sputtering deposition, controlling the magnetron sputtering deposition time to be 1h, cooling for 30min, and then preparing the Cu-CrSi metal composite film layer, wherein the thickness of the composite structure glue layer is controlled to be 12 microns.
Example 2: a loudspeaker diaphragm composite material.
The composition of the loudspeaker diaphragm composite material is basically the same as that of the loudspeaker diaphragm composite material in the embodiment 1, except that the thickness of the modified cellulose polyester composite film is controlled to be 5 micrometers, and a composite structure glue layer comprises the following components in percentage by mass: 60% of copper powder, 10% of polycaprolactone diol, 20% of p-phenylene diisocyanate, 1% of sealing agent diethyl malonate, 1% of cross-linking agent pentaerythritol, 0.5% of curing agent polythiol, 5% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 3% of ethylenediamine, wherein the thickness of a composite structure glue layer is 2 microns, the thickness of a metal composite film layer is 15 microns, and other technical characteristics are the same as those of the embodiment 1.
Example 3: a loudspeaker diaphragm composite material.
The composition of the loudspeaker diaphragm composite material is basically the same as that of the loudspeaker diaphragm composite material in the embodiment 1, except that the thickness of the modified cellulose polyester composite film is controlled to be 10 micrometers, and a composite structure glue layer comprises the following components in percentage by mass: 70% of copper powder, 12% of polycaprolactone diol, 14% of p-phenylene diisocyanate, 0.5% of blocking agent diethyl malonate, 2% of cross-linking agent pentaerythritol, 0.5% of curing agent polythiol, 1% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 1% of ethylenediamine, wherein the thickness of a composite structure glue layer is 5 micrometers, the thickness of a metal composite film layer is 11 micrometers, and the rest technical characteristics are the same as those of the embodiment 1.
Example 4: a loudspeaker diaphragm composite material.
The composition of the loudspeaker diaphragm composite material is basically the same as that of the loudspeaker diaphragm composite material in the embodiment 1, except that the thickness of the modified cellulose polyester composite film is controlled to be 10 micrometers, and a composite structure glue layer comprises the following components in percentage by mass: 63% of copper powder, 12% of polycaprolactone diol, 14% of p-phenylene diisocyanate, 1% of sealing agent diethyl malonate, 3% of cross-linking agent pentaerythritol, 1% of curing agent polythiol, 5% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt, 1% of ethylenediamine, 5 μm of composite structure glue layer, 15 μm of metal composite film layer and the like, wherein the rest technical characteristics are the same as those of the embodiment 1.
Comparative example 1
The modified cellulose polyester composite film of example 1 was replaced with an 8 μm PET film produced by Delui environmental protection materials science and technology Co., Ltd, available in Dongguan city, and a composite adhesive layer was directly coated on the surface of the PET film available in market, and the rest technical characteristics were the same as those of example 1.
Comparative example 2
The acrylic adhesive D-138 produced by New Material Ltd of spun Dai union, available in Dongguan city, was used in place of the composite structural adhesive in example 1, and the remaining technical characteristics were the same as those in example 1.
Comparative example 3
The metal composite film of example 1 was replaced with a 12 μm copper foil, and the technical characteristics were the same as those of example 1.
Performance testing
1. Adhesion force Performance test
The adhesive force was measured for the diaphragm composite materials prepared in examples 1 to 4 and comparative examples 1 to 3, in which: the adhesion was measured by the method of JISZ0237 standard.
2. High pressure resistance test
The breakdown voltage of the diaphragm composite material obtained in examples 1 to 4 and comparative examples 1 to 3 was measured using a 9635A high voltage tester manufactured by beijing, rd co-dell, pioneer science and technology ltd.
3. Internal damping test
The diaphragm composite materials prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to an elastic modulus (damping) test with reference to the damping performance test method of GBT18258-2000 damping material.
4. Burst strength test
The diaphragm composite materials prepared in examples 1 to 4 and comparative examples 1 to 3 were tested for burst strength using a fully intelligent burst strength tester produced by the Neurospermaceae family.
5. Fidelity frequency bandwidth test
The voice coil made of the diaphragm composite material prepared in examples 1 to 4 and comparative examples 1 to 3 was subjected to a fidelity band width test using Cooleditpro professional audio analysis software, and the width of the fidelity band of the diaphragm composite material (after exceeding the band width, sound distortion) was tested.
The test results of the diaphragm composite materials prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in table 1.
TABLE 1
As can be seen from the experimental data in table 1, the loudspeaker diaphragm composite materials in examples 1 to 4 prepared by the method of the present invention have a large elastic modulus, a small internal damping (the larger the elastic modulus is, the smaller the internal damping is), the smaller the internal damping is, the higher the sensitivity is, the better the sound quality effect is, and the fidelity band is large, the adaptability is strong, the breakdown voltage is high, and the burst strength is high. Comparing the data of example 1 and comparative example 1, it can be seen that the breakdown voltage of the modified cellulose polyester composite film prepared by the method of the present invention is increased and the width of the fidelity band is greatly increased compared with the conventional PET film for the compounding of the diaphragm, and thus it can be seen that the modified cellulose polyester composite film has a great influence on the width of the fidelity band. Comparing the data of the example 1 and the comparative example 2, it can be seen that the composite structural adhesive prepared by the method of the present invention can improve the adhesive force between the modified cellulose polyester composite film and the metal composite film layer, improve the width of the fidelity band, and have better sound transmission effect compared with the traditional acrylic adhesive for compounding the modified cellulose polyester composite film and the metal composite film. Comparing the data of example 1 and comparative example 3, it can be seen that the metal composite film prepared by the method of the present invention can greatly improve the breakdown voltage, the burst strength and the width of the fidelity band, increase the overall elastic modulus of the material, and improve the sensitivity of the audio frequency, compared with the conventional copper foil for compounding the diaphragm material.
This loudspeaker diaphragm combined material adopts modified cellulose polyester composite film bonding metal composite film's composite construction in addition, not only can effectively strengthen this loudspeaker diaphragm combined material's rigidity through metal composite film, the ability that the biggest vibration of reinforcing loudspeaker diaphragm combined material bore, higher elasticity has been remain through modified cellulose polyester composite film simultaneously, and can take place subtle co-vibration between modified cellulose polyester composite film (plastics material) and the metal composite film layer (metal material) among the vibration process, make this loudspeaker diaphragm combined material possess good transient state, sensitivity and frequency response, the tone quality is effectual.
The above description is only for the preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, and therefore, all equivalent or modifications that do not depart from the spirit of the present invention are intended to fall within the scope of the present invention.
Claims (7)
1. A loudspeaker diaphragm composite material, comprising:
the modified cellulose polyester composite film is prepared by the following method:
s11, weighing 100g of oven-dried needle leaf pulp, adding deionized water, stirring at a high speed to prepare 0.5 mass percent pulp, then adding 2g of TEMPO and 12g of NaBr, continuously stirring for 30min, then adding 6g of NaClO, continuously stirring for 30min, then gradually adding 0.5mol/L NaOH standard solution, and adjusting the pH to 10 to finish the reaction;
s12, adding 6ml of absolute ethyl alcohol to terminate the reaction, filtering and washing to obtain oxidized wet pulp, adding a proper amount of deionized water to adjust the pulp concentration to 1%, and carrying out high-pressure homogenization treatment for 4 times to obtain a TEMPO oxidized cellulose solution;
s13, placing the TEMPO oxidized cellulose solution prepared in the step S12 into a sand core funnel, performing suction filtration through a connected vacuum pump to obtain wet cellulose powder, taking out the wet cellulose powder, and drying the wet cellulose powder in an oven at 50 ℃ for 24 hours to obtain modified cellulose powder;
s14, weighing 100g of acrylic resin powder and 10g of the cellulose powder prepared in the step S13, mixing and crushing for 5min by a high-speed crusher, then melting and extruding the mixed powder material into a wire shape by a double-screw extruder, and finally cutting into particles by a cold granulator;
s15, adding the particles obtained in the step S14 into a biaxial stretching machine, and preheating, melting, stretching, shaping and cooling the particles through the biaxial stretching machine to obtain a modified cellulose polyester composite film;
coating the composite structure adhesive layer at the bottom of the modified cellulose polyester composite film;
the metal composite film layer is adhered to the bottom of the composite structure adhesive layer and is prepared by the following method:
s31, cutting the monocrystalline silicon piece into squares with the size of 20mm multiplied by 20mm, putting the squares into an ultrasonic cleaning instrument for ultrasonic cleaning for 20min, and cutting the copper piece with the thickness of 0.01mm into copper pieces with the specification of 500mm multiplied by 500mm for standby;
s32, mounting the CrSi target in a magnetron sputtering coating machine, and adjusting the distance between the CrSi target and the substrate to a proper position; taking out the basal disc, fixing the cut copper sheet on the basal disc, then placing the monocrystalline silicon wafer above the basal copper sheet, installing the basal disc, and closing the vacuum chamber;
s33, turning on a power supply and a circulating water system of the magnetron sputtering coating machine, pre-pumping to about 15Pa by using a mechanical pump, turning on a molecular pump to a high vacuum of 1.5 multiplied by 10-3Pa; then high-purity argon is introduced, the argon flow is set to be 45sccm, and a stop valve is adjusted to stabilize the air pressure in the vacuum chamber at 7 x 10-1Pa；
S34, turning on a direct current power supply, adjusting the sputtering current to 0.5A, and pre-sputtering for 2 min; and then opening a base plate rotating button, setting the rotating speed of the base plate to be 15r/min, opening a target material baffle, carrying out magnetron sputtering deposition, controlling the magnetron sputtering deposition time to be 1h, and cooling for 30min to obtain the Cu-CrSi metal composite film layer.
2. The loudspeaker diaphragm composite material of claim 1, wherein: the composite structure glue layer comprises the following components in percentage by mass: 60-70% of copper powder, 10-20% of polycaprolactone diol, 10-20% of p-phenylene diisocyanate, 0.5-1% of sealing agent diethyl malonate, 1-3% of cross-linking agent pentaerythritol, 0.5-1% of curing agent polythiol, 1-5% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 1-5% of ethylenediamine.
3. The loudspeaker diaphragm composite material of claim 2, wherein: the composite structure glue layer comprises the following components in percentage by mass: 65% of copper powder, 12% of polycaprolactone diol, 15% of p-phenylene diisocyanate, 0.8% of sealing agent diethyl malonate, 1.5% of cross-linking agent pentaerythritol, 0.9% of curing agent polythiol, 2% of chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt and 3% of ethylenediamine.
4. The loudspeaker diaphragm composite material of claim 3, wherein: the composite structure adhesive layer is prepared by the following method:
s21, pouring accurately weighed copper powder into 0.5mol/L diluted hydrochloric acid solution, stirring for 30min for surface treatment, washing with absolute ethyl alcohol solution for a plurality of times, and then drying in vacuum; then adding the treated copper powder into 1.2mol/L silane coupling agent solution, stirring for 20min to enable the copper powder to fully react, washing the copper powder for a plurality of times by using absolute ethyl alcohol solution after suction filtration, then carrying out suction filtration, and taking out the copper powder for later use after vacuum drying;
s22, adding polycaprolactone diol into a vacuum dehydration box, controlling the temperature at 100 ℃ for vacuum dehydration for 2 hours, then adding metered p-phenylene diisocyanate, maintaining the system at 80 ℃ for reaction for 3 hours to obtain a polyurethane prepolymer, then adding a chain extender N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium salt, ethylenediamine and a sealing agent diethyl malonate for continuous reaction for 2 hours, then adding a cross-linking agent pentaerythritol and a curing agent polythiol for continuous reaction for 2 hours to obtain a conductive composite structural adhesive base material;
s23, mixing the copper powder subjected to surface treatment in the step S21 with the conductive composite structural adhesive base material prepared in the step S22, defoaming in vacuum, and casting and molding at the temperature of 90 ℃ to prepare the high-polymerization polyurethane conductive composite structural adhesive;
s24, uniformly coating the polyurethane conductive composite structural adhesive prepared in the step S23 on the bottom of the modified cellulose polyester composite film by using a glue spreader to form a composite structural adhesive layer.
5. The loudspeaker diaphragm composite material of claim 1, wherein: the thickness of the modified cellulose polyester composite film is 5-10 mu m.
6. The loudspeaker diaphragm composite material of claim 1, wherein: the thickness of the composite structure glue layer is 2-5 mu m.
7. The loudspeaker diaphragm composite material of claim 1, wherein: the thickness of the metal composite film layer is 10-15 mu m.
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| CN114827879B (en) * | 2021-01-29 | 2023-08-08 | 歌尔股份有限公司 | Vibrating diaphragm and sound generating device |
| CN114827875B (en) * | 2021-01-29 | 2023-08-08 | 歌尔股份有限公司 | Vibrating diaphragm and sound generating device |
| CN114827877B (en) * | 2021-01-29 | 2023-08-08 | 歌尔股份有限公司 | Vibrating diaphragm and sound generating device |
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| CN114827878B (en) * | 2021-01-29 | 2023-08-08 | 歌尔股份有限公司 | Vibrating diaphragm and sound generating device |
| CN115589562B (en) * | 2022-10-19 | 2023-08-01 | 深圳市三诺数字科技有限公司 | Preparation method of composite loudspeaker diaphragm and related equipment thereof |
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