CN103525014B - Three-phase composite high-dielectric-property material, manufacturing method and processing method - Google Patents
Three-phase composite high-dielectric-property material, manufacturing method and processing method Download PDFInfo
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Abstract
The invention provides a three-phase composite high-dielectric-property material, a manufacturing method and a processing method. The three-phase composite high-dielectric-property material comprises surface-activated barium titanate, silicon package carbon blank and epoxy resin. The three-phase composite high-dielectric-property material is manufactured according to the following steps of (1) preprocessing barium titanate, (2) preprocessing carbon blank, (3) reprocessing powdery surface-oxidized carbon blank, (4) preprocessing epoxy resin and (5) taking and adding surface-activated barium titanate and silicon package carbon blank into a epoxy resin butanone solution. The processing method includes the following steps of (1) material preprocessing, (2) curing agent preprocessing, (3) copper foil preprocessing, (4) surface coating and (5) solidifying. According to the three-phase composite high-dielectric-property material, the manufacturing method and the processing method, under the premise that dielectric loss is controlled, conductive particles are used for replacing a part of ferroelectric ceramics to manufacture a conductor/ceramics/a polymer three-phase composite dielectric material, wherein the conductor/the ceramics/the polymer three-phase composite dielectric material can effectively improve the dielectric constant of a polymer matrix composite material. Meanwhile, the problems that carbon blank is difficult to disperse in a polymer and dielectric loss is increased due to the fact that a conductive path is formed after the content of the carbon blank rises are effectively solved.
Description
Technical field
The present invention relates to composite dielectric performance materials and preparation method thereof, process the field of the method for embed-type electrical condenser, particularly relate to three-phase composite material of polymer/inorganic dielectric particle/conducting particles and preparation method thereof, process the method for embed-type electrical condenser.
Background technology
Along with the fast development of science and technology, to the requirement miniaturization more of electronic product, lightness, low cost, multi-functional, high reliability.And in printed circuit board (PCB) (PCB), passive element is more than 20 times of active part, in occupation of the space of 40%, wherein capacitors count accounts for again four one-tenth of passive element, so electrical condenser in electronic product in occupation of critical role.At present, domesticly allly require high electronics and IT products manufacturing concern to miniaturization, multifunction, one of important developing direction replaces existing surface-mount type electrical condenser with embed-type components and parts.Therefore, the importance of embedded capacitor medium material seems particularly outstanding.
In existing capacitor dielectric material, " stupalith " has high dielectric property, low-loss advantage, but poor with pcb board bonding properties, and simultaneously powder is easily reunited, processing condition are harsh, and practical application has limitation.And " polymer materials " processing characteristics is good, cheap, and good with pcb board adhesive property, but its specific inductivity very low (general ε <5).Therefore, for obtaining the dielectric material having high dielectric property and excellent machinability concurrently, usually ferroelectric ceramic powder being filled in polymkeric substance in prior art and making ceramic/polymer composite.This type of method inserting the high ferroelectric ceramic powder of specific inductivity in polymeric matrix can improve the specific inductivity of matrix material.Relative to polymkeric substance, the specific inductivity being generally filled with the polymer matrix composite dielectric constant composite of ferroelectric ceramic(s) has tens times to the raising of hundred times.According to compound rule, if ceramic/polymer PMC will obtain higher specific inductivity, then ceramic composition content is generally very high, but reduce along with its dispersing property of increase of ceramic powder content, very easily produce more reunion, the dielectric loss of matrix material certainly will be increased, reduce processing characteristics largely simultaneously.Therefore, usually there is the deficiencies such as the low and difficult processing of specific inductivity not high enough (general ε <100), cohesiveness in ceramic/polymer composite.
In addition, also have a kind of electrical conductor/polymer composites in prior art, this type of electrical conductor-polymer composites to have close to unit for electrical property parameters during seepage flow threshold values at loading level and significantly raises.At present, conventional conductive filler for the preparation of conductor-polymer composites has Ag, Cu, Al, Ni, carbon black, Graphene etc., the electrode that the conductive particles itself such as Ag wherein, carbon black produce turns to Cloud Distribution distortion polarization, for elasticity, the instantaneous polarization completed, noenergy consumes, be filled in polymkeric substance and will form conductive particles/polymer interface, produce interfacial polarization.This type of be polarized in loading level low time make polymer matrix composite specific inductivity increase degree less, and when loading level increase to meet or exceed percolation threshold time, because the spacing between conductive particle is too small, the unbound electron of conductive particle will move between each conductive particle, form conductive path, under LCF effect, produce larger conductance loss, make conductor/polymer composites lose practical value.
Summary of the invention
The present invention is directed to above problem, provide a kind of method that still can keep the three-phase composite high dielectric property material of lower dielectric loss and excellent machinability, preparation method and process embed-type electrical condenser while improving material dielectric constant.
Three-phase composite high dielectric property material of the present invention: comprise surface active metatitanic acid barium 10-40 parts by volume, bag silicon carbon black 1-15 parts by volume and epoxy resin 45-89 parts by volume.
The preparation method of three-phase composite high dielectric property material of the present invention, with carbon black, barium titanate and epoxy resin for major ingredient, then, is prepared according to the following steps:
1) barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 1-2 weight% again, add in described silane coupling agent quality 18-25 dehydrated alcohol doubly and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed that 1-3 per second drips, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing;
2.1) massfraction carbon black being added 30-40 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 1-2h at 75-85 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until PH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 6-10h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) standby powdery surface oxygenated black quality 250-350 distilled water doubly and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 1-2h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for powdery surface oxygenated black quality 2-8 anion surfactant doubly, carry out ultrasonicly adding stirring, the time is 1-2h again;
3.3) and drip enters the silane coupling agent ethanol that ammoniacal liquor ethanol that 10-15 part volume percent is 40vol% and 10-15 part volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 10-20min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip the tetraethoxy ethanol that 40-60 part volume percent is 6vol% again, continue to stir 10-14h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of Surface coating silicon by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5) step 1.4 is got) obtained surface active metatitanic acid barium 10-40 parts by volume and step 3.5) obtained bag silicon carbon black 1-15 parts by volume adds in the obtained epoxy resin butanone solution 135-267 part of step 4), carries out ultrasonicly adding stirring, and the time is 1-2h; Obtained.
Described step 3.5) in suction method be: by 3.5) in obtain bag silicon carbon black solution pour in Backflow bottle, and the molarity adding 10-20 times of volume is the thanomin ethanolic soln of 3-4, make the two reflux under the condition of 85-95 DEG C 10-15h, finally obtain the bag silicon carbon black of powdery successively through centrifugal, ethanol purge and drying.
Described silane coupling agent model is KH550.
Described anion active agent is sodium laurylsulfonate.
Adopt the method for the embed-type electrical condenser of three-phase composite high dielectric property of the present invention materials processing, operate according to the following steps:
1) three-phase composite high dielectric property pretreatment: three-phase composite high dielectric property material is placed in stink cupboard, heats and stir, the time is 1-2h, and temperature is 50-80 DEG C; Heat preservation for standby use;
2) solidifying agent pre-treatment: solidifying agent being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain solidifying agent butanone solution, stand-by;
3) Copper Foil pre-treatment: get two panels Copper Foil, put into dehydrated alcohol, and clean 0.8-1.2h in ultrasonic cleaner; Again Copper Foil is heated to 130-150 DEG C; Finally be cooled to room temperature;
4) apply: first, with the ratio that solidifying agent and epoxy resin mass ratio are 0.8:1, while stirring solidifying agent butanone solution is dropwise added in pretreated three-phase composite high dielectric property material, obtain three-phase composite high dielectric property material paste, then three-phase composite high dielectric property material paste is evenly coated in the surface of a Copper Foil;
5) solidify: the Copper Foil being coated with three-phase composite slurry is placed in preliminary drying 4-6min under 50-70 DEG C of environment, then fits together with another sheet Copper Foil, make coat be clipped between two panels Copper Foil; Hot pressing 5-15s under pressure 0.5-1.5MPa, temperature 120-140 DEG C condition; Dry 15-25min under being finally placed in 120-140 DEG C of environment, obtain the embed-type electrical condenser of three-phase composite medium; Complete.
Described solidifying agent is polyamide resin.
The present invention under control dielectric loss prerequisite, a kind of conductor/ceramic/polymer three-phase composite dielectric material that effectively can improve the specific inductivity of polymer matrix composite that utilized conductive particle Substitute For Partial ferroelectric ceramic(s) to prepare.For conductive particle wherein, especially cheap with the price of carbon black again, carbon black also more easily prepares the product of form of diverse; Simultaneously, this case is by the step 2 of preparation technology), the process of step 3) and suction method, silicon oxide layer on carbon blacksurface is coated, thus to efficiently solve carbon black difficulties in dispersion and content of carbon black easily form the problem that conductive path increases dielectric loss after rising in the polymer simultaneously.
Principle of the present invention is: utilize modification to make carbon black, barium titanate and polymkeric substance have better consistency and connectivity, makes carbon black not easily form energising network simultaneously (be embodied in and adopt anion surfactant, silane coupling agent in the step 3) of preparation method, silicon source is hydrolyzed at carbon blacksurface, polycondensation becomes unsetting SiO by the integument of silicon oxide
2layer), thus the dielectric loss that reduction carbon black brings as filler.And controlled by each component of matrix material, comprise and the adjustment of amounts of carbon black and barium titanate amount is improved dielectric properties.
The present invention has following effect:
1. the invention enables carbon black to have more excellent dispersiveness in the polymer, parcel property is better, and loss is lower.
2. carbon black/barium titanate/polymkeric substance that prepared by the present invention has excellent dielectric properties and low-loss.
3. preparation method provided by the invention, technique is simple, with low cost, mold temperature is low.
4. the three-phase composite material that prepared by the present invention all accords with the dielectric material application of embed-type electrical condenser from dielectric properties and processing characteristics two aspect.
Accompanying drawing explanation
Fig. 1 is material of the present invention preparation, work flow schematic diagram,
Fig. 2 is the flow process chart of carbon blacksurface modification in the present invention,
Fig. 3 a is the microtexture Electronic Speculum figure mono-of three-phase composite material of the present invention,
Wherein BaTiO
3loading level is 20vol%, CB@SiO
2loading level is 5vol%;
Fig. 3 b is the microtexture Electronic Speculum figure bis-of three-phase composite material of the present invention,
Wherein BaTiO
3loading level is 20vol%, CB@SiO
2loading level is 15vol%;
Fig. 4 a is that three-phase composite material of the present invention adopts different black loading to the influence curve figure of specific inductivity;
Fig. 4 b is that three-phase composite material of the present invention adopts different black loading to the influence curve figure of dielectric loss;
Fig. 5 a is that three-phase composite material of the present invention adopts different Filled with Barium Titanate amount to the influence curve figure of specific inductivity;
Fig. 5 b is that three-phase composite material of the present invention adopts different Filled with Barium Titanate amount to the influence curve figure of dielectric loss.
Embodiment
Three-phase composite high dielectric property material of the present invention after hardening, comprises surface active metatitanic acid barium 10-40 parts by volume, bag silicon carbon black 1-15 parts by volume and epoxy resin 45-89 parts by volume.Its microtexture is as shown in Fig. 3 a, 3b; Its dielectric properties are as shown in Fig. 4 a, 4b, 5a, 5b.
The preparation method of three-phase composite high dielectric property material of the present invention, with carbon black, barium titanate and epoxy resin for major ingredient, general technical route (preparation method's flow process) as shown in Figure 1, is prepared according to the following steps:
1) barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 1-2 weight% again, add in described silane coupling agent quality 18-25 dehydrated alcohol doubly and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed that 1-3 per second drips, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing; As shown in Figure 2,
2.1) massfraction carbon black being added 30-40 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 1-2h at 75-85 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until PH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 6-10h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) standby powdery surface oxygenated black quality 250-350 distilled water doubly and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 1-2h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for powdery surface oxygenated black quality 2-8 anion surfactant doubly, carry out ultrasonicly adding stirring, the time is 1-2h again;
3.3) and drip enters the silane coupling agent ethanol that ammoniacal liquor ethanol that 10-15 part volume percent is 40vol% and 10-15 part volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 10-20min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip the tetraethoxy ethanol that 40-60 part volume percent is 6vol% again, continue to stir 10-14h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of Surface coating silicon by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5) step 1.4 is got) obtained surface active metatitanic acid barium 10-40 parts by volume and step 3.5) obtained bag silicon carbon black 1-15 parts by volume adds in the obtained epoxy resin butanone solution 135-267 part of step 4), carries out ultrasonicly adding stirring, and the time is 1-2h; Obtained.
Described step 3.5) in suction method be: by 3.5) in obtain bag silicon carbon black solution pour in Backflow bottle, and the molarity adding 10-20 times of volume is the thanomin ethanolic soln of 3-4, make the two reflux under the condition of 85-95 DEG C 10-15h, finally obtain the bag silicon carbon black of powdery successively through centrifugal, ethanol purge and drying.
Described silane coupling agent model is KH550.
Described anion active agent is sodium laurylsulfonate.
The raw material that employing technique scheme obtains, to process the method (i.e. working method) of embed-type electrical condenser, operates according to the following steps:
1) three-phase composite high dielectric property pretreatment: three-phase composite high dielectric property material is placed in stink cupboard, heats and stir, the time is 1-2h, and temperature is 50-80 DEG C; Heat preservation for standby use;
2) solidifying agent pre-treatment: solidifying agent being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain solidifying agent butanone solution, stand-by;
3) Copper Foil pre-treatment: get two panels Copper Foil, put into dehydrated alcohol, and clean 0.8-1.2h in ultrasonic cleaner; Again Copper Foil is heated to 130-150 DEG C; Finally be cooled to room temperature;
4) apply: first, with the ratio that solidifying agent and epoxy resin mass ratio are 0.8:1, while stirring solidifying agent butanone solution is dropwise added in pretreated three-phase composite high dielectric property material, obtain three-phase composite high dielectric property material paste, then three-phase composite high dielectric property material paste is evenly coated in the surface of a Copper Foil;
5) solidify: the Copper Foil being coated with three-phase composite slurry is placed in preliminary drying 4-6min under 50-70 DEG C of environment, then fits together with another sheet Copper Foil, make coat be clipped between two panels Copper Foil; Hot pressing 5-15s under pressure 0.5-1.5MPa, temperature 120-140 DEG C condition; Dry 15-25min under being finally placed in 120-140 DEG C of environment, obtain the embed-type electrical condenser of three-phase composite medium; Complete.
Described solidifying agent is polymeric amide subresin.
In final obtained electrical condenser, the microtexture of material is as shown in Fig. 3 a, 3b, wherein BaTiO
3loading level is 20vol%, bag silicon carbon black (CB@SiO
2) loading level 3a is 5vol%; 3b is 15vol%.As can be seen from the figure, BaTiO
3particle (brightness large, size at about 500nm) is scattered in Epoxy comparatively equably, and there is a fuzzy transition layer at particle and Epoxy interface.Illustrate through KH550 surface modification, make BaTiO
3particle surface functional group can be connected preferably with Epoxy (occur that chemistry connects), and therefore interface firmly, can reduce spatial polarizations to a certain extent, thus makes the dielectric loss of matrix material maintain a lower level.Meanwhile, CB@SiO
2be distributed in Epoxy, its particle diameter <100nm, at CB@SiO
2when content is lower (as Fig. 3 a) because carbon black pellet size is little, and carbon black and Epoxy do not have obvious interface, substantially can't see CB@SiO
2the existence of particle.As CB@SiO
2when content is higher, (as Fig. 3 b) can see, carbon black pellet is scattered in Epoxy more uniformly, does not occur in BaTiO
3the enrichment at-Epoxy interface, illustrates that the carbon black after coating modification and Epoxy have stronger consistency.CB@SiO
2-Epoxy interface is fuzzy, is the carbon blacksurface transition layer because the process of carbon blacksurface bag silicon is formed, i.e. the SiO of unsetting form
2the existence of layer, and in transition layer, remained the relevant group of tensio-active agent, thus it is connected closely with Epoxy.
In conjunction with specific embodiments preparation method is further illustrated again below.
Embodiment one: be prepared according to the following steps:
1) barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 1weight% again, add in the dehydrated alcohol of described silane coupling agent quality 18 times and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed of 1 per second, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing; As shown in Figure 2,
2.1) massfraction carbon black being added 30 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 1h at 75 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until PH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 6h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) distilled water of standby powdery surface oxygenated black quality 250 times and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 1h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for the anion surfactant (SDS) of powdery surface oxygenated black quality 2 times, carry out ultrasonicly adding stirring, the time is 1h again;
3.3) and drip enters silane coupling agent (KH550) ethanol that ammoniacal liquor ethanol that 10 parts of volume percent are 40vol% and 10 parts of volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 10min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip tetraethoxy (TEOS) ethanol that 40 parts of volume percent are 6vol% again, continue to stir 10h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of the Surface coating silicon of powdery by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5), step 1.4 is got) obtained surface active metatitanic acid barium 20 parts by volume and step 3.5) obtained bag silicon carbon black 13 parts by volume adds in the obtained epoxy resin butanone solution 201 parts of step 4), carries out ultrasonicly adding stirring, and the time is 1h; Obtained.
Embodiment two: be prepared according to the following steps:
1), barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 2 weight% again, add in the dehydrated alcohol of described silane coupling agent quality 25 times and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed of 3 per second, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing; As shown in Figure 2,
2.1) massfraction carbon black being added 40 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 2h at 85 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until PH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 10h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) distilled water of standby powdery surface oxygenated black quality 350 times and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 2h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for the anion surfactant of powdery surface oxygenated black quality 8 times, carry out ultrasonicly adding stirring, the time is 2h again;
3.3) and drip enters silane coupling agent (KH550) ethanol that ammoniacal liquor ethanol that 15 parts of volume percent are 40vol% and 15 parts of volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 20min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip tetraethoxy (TEOS) ethanol that 60 parts of volume percent are 6vol% again, continue to stir 14h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of the Surface coating silicon of powdery by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5) step 1.4 is got) obtained surface active metatitanic acid barium 30 parts by volume and step 3.5) obtained bag silicon carbon black 10 parts by volume adds in the obtained epoxy resin butanone solution 180 parts of step 4), carries out ultrasonicly adding stirring, and the time is 2h; Obtained.
Embodiment three: be prepared according to the following steps:
1), barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 1.5 weight% again, add in the dehydrated alcohol of described silane coupling agent quality 22 times and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed of 2 per second, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing; As shown in Figure 2,
2.1) massfraction carbon black being added 35 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 1.5h at 80 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until PH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 8h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) distilled water of standby powdery surface oxygenated black quality 300 times and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 1.5h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for the anion surfactant (SDS) of powdery surface oxygenated black quality 5 times, carry out ultrasonicly adding stirring, the time is 1.5h again;
3.3) and drip enters silane coupling agent (KH550) ethanol that ammoniacal liquor ethanol that 13 parts of volume percent are 40vol% and 13 parts of volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 15min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip tetraethoxy (TEOS) ethanol that 50 parts of volume percent are 6vol% again, continue to stir 12h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of the Surface coating silicon of powdery by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5), step 1.4 is got) obtained surface active metatitanic acid barium 10 parts by volume and step 3.5) obtained bag silicon carbon black 10 parts by volume adds in the obtained epoxy resin butanone solution 240 parts of step 4), carries out ultrasonicly adding stirring, and the time is 1.5h; Obtained.
Below the portion of techniques feature in above-mentioned 3 embodiments is described further:
Described step 3.5) in suction method be: by 3.5) in obtain bag silicon carbon black solution pour in Backflow bottle, and the molarity adding 10-20 times of volume is the thanomin ethanolic soln of 3-4, make the two reflux under the condition of 85-95 DEG C 10-15h, finally obtain the bag silicon carbon black of powdery successively through centrifugal, ethanol purge and drying.
Described silane coupling agent model is KH550.
Described anion active agent is sodium laurylsulfonate.
In conjunction with specific embodiments working method is further illustrated (solidifying agent in following is polymeric amide subresin) more below.
Embodiment a: the method for processing embed-type electrical condenser, operates according to the following steps:
1) three-phase composite high dielectric property pretreatment: three-phase composite high dielectric property material is placed in stink cupboard, heats and stir, the time is 1h, and temperature is 50 DEG C; Heat preservation for standby use;
2) solidifying agent pre-treatment: solidifying agent being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain solidifying agent butanone solution, stand-by;
3) Copper Foil pre-treatment: get two panels Copper Foil, put into dehydrated alcohol, and clean 0.8h in ultrasonic cleaner; Again Copper Foil is heated to 130 DEG C; Finally be cooled to room temperature;
4) apply: first, with the ratio that solidifying agent and epoxy resin mass ratio are 0.8:1, while stirring solidifying agent butanone solution is dropwise added in pretreated three-phase composite high dielectric property material, obtain three-phase composite high dielectric property material paste, then three-phase composite high dielectric property material paste is evenly coated in the surface of a Copper Foil;
5) solidify: the Copper Foil being coated with three-phase composite slurry is placed in preliminary drying 4min under 50 DEG C of environment, then fits together with another sheet Copper Foil, make coat be clipped between two panels Copper Foil; At pressure 0.5MPa, hot pressing 5s under temperature 120 DEG C of conditions; Dry 15min under being finally placed in 120 DEG C of environment, obtain the embed-type electrical condenser of three-phase composite medium; Complete.
Embodiment b: the method for processing embed-type electrical condenser, operates according to the following steps:
1) three-phase composite high dielectric property pretreatment: three-phase composite high dielectric property material is placed in stink cupboard, heats and stir, the time is 2h, and temperature is 80 DEG C; Heat preservation for standby use;
2) solidifying agent pre-treatment: solidifying agent being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain solidifying agent butanone solution, stand-by;
3) Copper Foil pre-treatment: get two panels Copper Foil, put into dehydrated alcohol, and clean 1.2h in ultrasonic cleaner; Again Copper Foil is heated to 150 DEG C; Finally be cooled to room temperature;
4) apply: first, with the ratio that solidifying agent and epoxy resin mass ratio are 0.8:1, while stirring solidifying agent butanone solution is dropwise added in pretreated three-phase composite high dielectric property material, obtain three-phase composite high dielectric property material paste, then three-phase composite high dielectric property material paste is evenly coated in the surface of a Copper Foil;
5) solidify: the Copper Foil being coated with three-phase composite slurry is placed in preliminary drying 6min under 70 DEG C of environment, then fits together with another sheet Copper Foil, make coat be clipped between two panels Copper Foil; At pressure 1.5MPa, hot pressing 15s under temperature 140 DEG C of conditions; Dry 25min under being finally placed in 140 DEG C of environment, obtain the embed-type electrical condenser of three-phase composite medium; Complete.
Embodiment c: the method for processing embed-type electrical condenser, operates according to the following steps:
1) three-phase composite high dielectric property pretreatment: three-phase composite high dielectric property material is placed in stink cupboard, heats and stir, the time is 1.5h, and temperature is 65 DEG C; Heat preservation for standby use;
2) solidifying agent pre-treatment: solidifying agent being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain solidifying agent butanone solution, stand-by;
3) Copper Foil pre-treatment: get two panels Copper Foil, put into dehydrated alcohol, and clean 1h in ultrasonic cleaner; Again Copper Foil is heated to 140 DEG C; Finally be cooled to room temperature;
4) apply: first, with the ratio that solidifying agent and epoxy resin mass ratio are 0.8:1, while stirring solidifying agent butanone solution is dropwise added in pretreated three-phase composite high dielectric property material, obtain three-phase composite high dielectric property material paste, then three-phase composite high dielectric property material paste is evenly coated in the surface of a Copper Foil;
5) solidify: the Copper Foil being coated with three-phase composite slurry is placed in preliminary drying 5min under 60 DEG C of environment, then fits together with another sheet Copper Foil, make coat be clipped between two panels Copper Foil; At pressure 1MPa, hot pressing 10s under temperature 130 DEG C of conditions; Dry 20min under being finally placed in 130 DEG C of environment, obtain the embed-type electrical condenser of three-phase composite medium; Complete.
In experiment, we find:
When barium carbonate powder volume content is fixed as 20vol%, three-phase composite material specific inductivity (Fig. 4 a) and dielectric loss (Fig. 4 b) with the change curve of bag silicon content of carbon black.From Fig. 4 a, when barium titanate content is fixed, the specific inductivity of three-phase composite material increases along with the increase of bag silicon content of carbon black, and bag silicon content of carbon black reaches the seepage flow threshold values of matrix material at 13vol%, and the specific inductivity of matrix material rapidly increases.Under 100Hz, along with bag silicon content of carbon black is increased to 13vol% from 0vol%, the specific inductivity of matrix material is increased to 63 from 13, adds nearly 5 times; Under 10KHz, matrix material specific inductivity is increased to 39 from 11, adds nearly 4 times.From Fig. 4 b, along with the increase of bag silicon content of carbon black, the dielectric loss of matrix material first reduces rear increase, near 5vol%, reach mnm., rapidly increasing close to during seepage flow threshold values.When bag silicon content of carbon black is less than 13vol%, under 10KHz, the dielectric loss of matrix material fluctuates near 0.03, and under 100Hz, the dielectric loss of matrix material is less than 0.08.
When bag silicon content of carbon black is fixed as 10vol%, the specific inductivity of three-phase composite material (Fig. 5 a) and dielectric loss (Fig. 5 b) with the graphic representation of barium titanate content.As we can see from the figure, along with the increase of barium titanate content, specific inductivity, dielectric loss also have obvious increase.As we know from the figure, under 1KHz, when barium titanate content is lower than 30vol%, along with barium titanate content is increased to 30vol% from 10vol%, the specific inductivity of three-phase composite material is increased to 62.7 from 15.7, and dielectric loss is increased to 0.0632 from 0.0342.And barium titanate content is when being 40vol%, the specific inductivity of matrix material increase sharply be 621.43 but dielectric loss also to increase sharply be 0.342.
Material prepared by the present invention, is guaranteeing outside excellent dielectric performance, is that specific inductivity is larger relative to the advantage of polymeric media material; Be have certain toughness relative to the advantage of ceramic medium material, processing characteristics is better, good shaping, and the base material with circuit card is consistent, and thermal property aspect is more mated; Be the suitable adjustment by pottery and conductor two kinds of weighting material proportionings relative to the advantage of ceramic-polymer complex media and conductor-polymkeric substance complex media, can while acquisition high dielectric constant the lower dielectric loss of guarantee and good processing characteristics.
In above embodiment, part starting material situation is as follows:
1. polymer matrix material:
Bis phenol-a epoxy resins (Epoxy) model: E44, epoxy equivalent (weight): 0.45mol/100g, by Guangzhou, east wind Chemical Co., Ltd. provides.
2. solidifying agent: polymeric amide subresin, itself and epoxy resin mass ratio are 0.8:1, and by Guangzhou, east wind Chemical Co., Ltd. provides.
3. electrical-conductive nanometer carbon black: model is Sweden SPC graphitized carbon black CB3100, and CTAB adsorptive value is 1100mg/g, and electric conductivity is about 0.1 Ω/cm3, and primary particle diameter is about 45nm.By Dongguan, Sheng Mao rubber-plastics material company limited provides.
4. barium carbonate powder (BaTiO3): median size is about 500nm, is provided by skill limited-liability company of FENGHUA ADVANCED TECHNOLOGY of Guangdong Province.
Claims (4)
1. a preparation method for three-phase composite high dielectric property material, described three-phase composite high dielectric property material comprises surface active metatitanic acid barium 10-40 parts by volume, bag silicon carbon black 1-15 parts by volume and epoxy resin 45-89 parts by volume; It is characterized in that, with carbon black, barium titanate and epoxy resin for major ingredient, then, be prepared according to the following steps:
1) barium titanate preprocessing;
1.1) barium titanate of powder shaped is added in dehydrated alcohol, Homogeneous phase mixing, obtain suspension;
1.2) get the silane coupling agent accounting for described barium titanate powder weight 1-2 weight% again, add in described silane coupling agent quality 18-25 dehydrated alcohol doubly and dilute, obtain activation diluent;
1.3) described activation diluent is added dropwise in aforementioned suspension with the speed that 1-3 per second drips, uniform stirring while dropping, carries out centrifugal treating immediately;
1.4) dry after centrifugal treating, obtain surface active metatitanic acid barium;
2) carbon black preprocessing;
2.1) massfraction carbon black being added 30-40 times of quality is in the nitric acid of 34%, and Homogeneous phase mixing, carries out water-bath, and stir 1-2h at 75-85 DEG C; Obtain acidic carbon black suspension;
2.2) add distilled water in oxytropism carbon black suspension, carry out centrifugal treating immediately, repeated multiple times until pH=7, obtain neutral carbon black suspension;
2.3) by neutral carbon black suspension drying treatment 6-10h in an oven; Obtain powdery surface oxygenated black;
3) powdery surface oxygenated black reprocessing;
3.1) standby powdery surface oxygenated black quality 250-350 distilled water doubly and the dehydrated alcohol with the quality such as distilled water, add powdery surface oxygenated black in distilled water-alcohol mixeding liquid; Carry out ultrasonicly adding stirring, the time is 1-2h; Obtain powdery surface oxygenated black water-ethanol suspension;
3.2) add in powdery surface oxygenated black water-ethanol suspension for powdery surface oxygenated black quality 2-8 anion surfactant doubly, carry out ultrasonicly adding stirring, the time is 1-2h again;
3.3) and drip enters the silane coupling agent ethanol that ammoniacal liquor ethanol that 10-15 part volume percent is 40vol% and 10-15 part volume percent are 16vol%, carry out ultrasonicly adding stirring, the time is 10-20min;
3.4) after upper step two kind of an additive instills completely, keep whipped state to drip the tetraethoxy ethanol that 40-60 part volume percent is 6vol% again, continue to stir 10-14h;
3.5) carry out centrifugation, ethanol purge and recentrifuge process again, obtain bag silicon carbon black solution; Finally bag silicon carbon black solution is obtained to the bag silicon carbon black of Surface coating silicon by suction method, stand-by;
4) epoxy resin pre-treatment: epoxy resin being added volume is in its butanone of 2 times, and is stirred to abundant dissolving; Obtain epoxy resin butanone solution;
5) step 1.4 is got) obtained surface active metatitanic acid barium 10-40 parts by volume and step 3.5) obtained bag silicon carbon black 1-15 parts by volume adds in the obtained epoxy resin butanone solution 135-267 part of step 4), carries out ultrasonicly adding stirring, and the time is 1-2h; Obtained.
2. the preparation method of three-phase composite high dielectric property material according to claim 1, it is characterized in that, described step 3.5) in suction method be: by 3.5) in obtain bag silicon carbon black solution pour in Backflow bottle, and the molarity adding 10-20 times of volume is the thanomin ethanolic soln of 3-4, make the two reflux under the condition of 85-95 DEG C 10-15h, finally obtain the bag silicon carbon black of powdery successively through centrifugal, ethanol purge and drying.
3. the preparation method of three-phase composite high dielectric property material according to claim 1, is characterized in that, described silane coupling agent model is KH550.
4. the preparation method of three-phase composite high dielectric property material according to claim 1, is characterized in that, described anion active agent is sodium laurylsulfonate.
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