CN102590047B - Dispersion measurement method of inorganic nano-particle composite polyimide film raw material - Google Patents
Dispersion measurement method of inorganic nano-particle composite polyimide film raw material Download PDFInfo
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Abstract
The invention relates to a dispersion measurement method of an inorganic nano-particle composite polyimide film raw material, comprising the following steps of: (1) placing a proper amount of a sample into a measurement container and then placing a metal plate electrode into the measurement container; (2) applying an alternative current voltage on two electrode plates, gradually increasing the voltage amplitude and recording a breakdown voltage measurement value; ( 3) comparing the measurement value with the standard value and analyzing; and (4) analyzing the measurement result, wherein the closer the measurement value and the standard value are, the more uniform the dispersion of the nano particles in the sample is. The time is saved, the dispersion is directly measured free from the limit of various dispersion stability mechanisms, the experiment device is simple, the measurement operation is convenient, and the experiment result is visual and accurate. The dispersion measurement method is mainly used in the technical field of the electronic insulation.
Description
Technical field
The present invention relates to a kind of dispersed detection method of inorganic nanoparticles, relate to or rather the dispersed detection method of a kind of inorganic nanoparticles compound polyimide film raw material, belong to the electric insulation technical field.
Background technology
In recent years, the usable range of variable-frequency motor was more and more wider.Efficiently, energy-conservation, being easy to the advantages such as control makes variable-frequency motor that alternative DC speed regulation trend be arranged greatly in metallurgy, lifting, all fields of locomotive traction, since particularly igbt (IGBT) comes out, the 10-20K left and right is brought up in the 1-2K left and right of carrier frequency during from bipolar transistor (GTR), and electrical machine insulation has been brought outstanding problem.A large amount of momentary pulse peak voltages are applied in turn-to-turn (particularly first circle) insulation, cause electrical machine insulation to damage too early, have a strong impact on running reliability of motor.In view of this, U.S.'s NEMA standard has been done corresponding change, to the examination of general service motor by MG1, Part30 (peak value 1000V, 2us rise time) changes MG1, Part31 (peak value 1600V into, 0.1us the rise time), improved requirement to the anti-high-frequency impulse of motor turn-to-turn insulation.
In the electric insulation technical field, organic film kind commonly used is a lot, mainly contains polyester (polyethylene terephthalate) film, polypropylene film, polyvinyl chloride film, polyethylene film, plasticon, Kapton etc.Wherein, polyimide (PI) is a kind of the highest macromolecular material of temperature classification of industrial widespread use, and the excellent performance that it at high temperature possesses can match in excellence or beauty with some Metal Phase.In addition, it also has good chemical stability, toughness, wearing quality, anti-flammability, electrical insulating property and other mechanical property.The combination property of above excellence, make polyimide be known as to surmount the material in epoch, is the first-selection of organic film in the electric insulation technical field.
Along with the develop rapidly of modernization industry, also more and more higher to the requirement of material property.But generally contain phenyl ring and imide ring structure on the PI molecular backbone, due to electron polarization and crystallinity, causing PI to exist between stronger strand acts on, cause that the PI strand is tightly packed, thereby cause the obvious water absorptivity of PI and thermal expansivity, cause PI film corona resistance very weak, this has limited its application under high temperature and accurate state.For meeting the wide market demands of variable-frequency motor, the electromagnetic wire industry must be made great efforts exploitation and be adapted to high-frequency pulse voltage, the electromagnetic wire of anti-corona.For the high-pressure frequency-conversion motor, must develop the Kapton (CRPI film) of anti-corona, make winding wire with it, to solve the not weakness of anti-corona of common PI film.
Inorganic nano-particle, owing to having unique character such as " size effect ", " interfacial effect " and " tunnel effect ", has all shown larger advantage at the aspects such as heat resistance, mechanical property and dimensional stability that improve material.Therefore study inorganic nano-particle (SiO
2, TiO
2, SiO
2/ TiO
2, Al
2O
3Deng) have important theory significance and using value in the application of modified polyimide (PI).The corona resistance of Polyamide/mineral Nanocomposite and physical strength and toughness all improve significantly than pure polyimide, and make material obtain outstanding performance because nanoscale both is compound.
At present, the preparation method of Polyamide/mineral Nanocomposite mainly contains sol-gel (Sol-gel) method, in-situation method and graft process.
Polyamide/mineral Nanocomposite is widely used: can be used as gas separation membrane, sensitization compound substance, microelectronic component, wrappage, also can be used for friction field.
Although, nano particle particularly all improves significantly and improves in the aspects such as thermal behavior, mechanical property and permeability the performance of PI, but the inorganic nano-particle in the PI/ inorganic nano composite material does not reach whole nanoscale yet to be disperseed, just certain a part of nano-dispersed.This is because the size of nano particle is little, there are a large amount of unsaturated links in surface, surfactivity is very large, belong to thermodynamic unstable system, particle coagulation, agglomeration very easily occur in preparation process or in last handling process, form second particle, make particle diameter become large, finally lose in use the peculiar function that nano particle possesses.And the dispersion stabilization of nano particle in inorganic nanoparticles compound polyimide film raw material directly determining the corona-resistance property of inorganic nanoparticles compound polyimide film.Therefore, the dispersion process of research nano particle in medium, prevent nanoparticle agglomerates, and the inorganic nanoparticles compound polyimide film raw material that obtains the nano particle good dispersion is most important.
The reunion of nano particle can be divided into two kinds: soft-agglomerated and hard aggregation.Soft-agglomerated is mainly by due to intergranular electrostatic force and Van der Waals force, because acting force is weak, can eliminate by some chemical actions or the mode that applies mechanical energy.The reason that hard aggregation forms except electrostatic force and Van der Waals force, also have chemical b `, so hard agglomeration is survivable, need to take some special methods to control.In preparing the process of nano particle, if do not adopt the dispersion measure, particle agglomeration will be very serious, can not reach the basic demand of nanometer powder, not realize the specific function of nanometer powder.Therefore studying the reunion of nano particle controls the nanometer powder preparation very important.
The reason that causes nanoparticle agglomerates is a lot, and being summed up is mainly the special surface structure that has due to nano particle, is existing the interaction energy-a nanoaction (F that is different between conventional particle (particle) between particle
n), nanoaction is the internal factor that nano particle is easily reunited, and obtain that good dispersion, particle diameter are little, the nano particle of narrow diameter distribution, must weaken or reduce nanoaction.Pursue the proper method when nano particle is carried out dispersion treatment, nano grain surface produces the solvation membrane interaction can (F
s), the electrostatic double layer electrostatic interaction can (F
r), the space protection interaction energy (F of Polymer adsorption layer
p) etc.In certain system, nano particle should be the equilibrium state that is in these several interaction energies, works as F
x＞F
s+ F
r+ F
pThe time, nano particle is easily reunited, and works as F
m＜F
s+ F
r+ F
pThe time, nano particle easily disperses.In addition, intermolecular force, electrostatic interaction, active high chemical bond (as hydrogen bond) are also the key factors that causes nanoparticle agglomerates usually, in nano particle small-medium size effect and surface effect, show more strongly., because the quantum tunneling effect of nano particle, electric charge shift and the intercoupling of interface atom, make nano particle very easily by interface, interaction occur and solid phase reaction is reunited., because of its high surface energy and larger contact interface, the speed of grain growth is accelerated, thereby particle size is difficult to remain unchanged.Some nano particle is (as CaCO
3) due to hydrolytic action, surface is stronger alkalescence, hydroxyl and water of coordination molecule, they can, by hydroxyl and the condensation of water of coordination molecule, generate hard aggregation.
The dispersion process of nano particle in liquid medium, the dispersion process of conventional granulates in liquid medium that can use for reference the comparative maturity that has proposed is theoretical.The dispersion process of conventional granulates in liquid medium is divided into 3 stages: wetting, dispersion and stable.Different from conventional granulates is, nano particle is that size reaches nano level solid particle, therefore the dispersion process of nano particle in liquid medium also can be thought minute these 3 stages: 1. wetting (nano particle is immersed in wetting in liquid medium, belongs to and soaks) of nano particle; 2. the dispersion of nano particle or cracked (by external influence power, making larger aggregation be separated into less nano particle); 3. nano particle stablizes (the assurance nano particle keeps dispersed for a long time in liquid phase, prevent that the nano particle that has disperseed from reassembling).
, according to the difference of Dispersing Methods, can be divided into physical dispersion and chemical dispersion.
1. physical dispersion
The physical dispersion method mainly contains 3 kinds: mechanical raking is disperseed, ultrasound wave disperses and the high power treatment method is disperseed.
1) mechanical raking is disperseed
It is a kind of simple physical dispersion that mechanical raking is disperseed, and is mainly by mechanical energy such as extraneous shearing force or impacts, and nano particle is fully disperseed in medium.In fact, this is a very complicated dispersion process, that this special phenomenon is referred to as mechanochemical effect by dispersed system being applied physics, the chemical property that mechanical force causes material in system and the series of chemical of following, reaching the dispersion purpose.The concrete form that mechanical raking is disperseed has grinding distribution, colloid mill dispersion, ball milling dispersion, high-speed stirred etc.Under mechanical raking, the special surface structure of nano particle easily produces chemical reaction, is formed with organic compounds side chain or protective seam nano particle is more easily disperseed.
2) ultrasound wave disperses
It is the effective ways that reduce nanoparticle agglomerates that ultrasound wave disperses, and it is relevant with cavitation that its mechanism of action is thought.The localized hyperthermia, high pressure or strong shock wave and the microjet etc. that utilize ultrasonic cavitation to produce, can weaken the nanoaction between nano particle greatly, effectively prevents nanoparticle agglomerates and make it abundant dispersion.Ultrasound wave has vital role to synthetic, the degraded of polymkeric substance of compound, the dispersion of particulate matter, and larger ultrasonic power can more effectively destroy intergranular reunion.But when disperseing, ultrasound wave should avoid ultrasonic time to cross cause for a long time overheated, because along with the rising of temperature, the probability of particle collision also increases, and can further aggravate on the contrary to reunite.Therefore, should select suitable ultrasonic jitter time.
3) the high power treatment method is disperseed
The high power treatment method is by the high energy particle effect, at nano grain surface, produces active site, increases surfactivity, makes it easily and other material generation chemical reactions or adhere to, and the nano grain surface modification is reached the purpose of easy dispersion.High energy particle comprises corona, ultraviolet light, microwave, plasma ray etc.
2. chemical dispersion
Chemical dispersion is in fact to utilize the surface chemistry method to add surface conditioning agent to realize the method for disperseing.Can change surface structure and the state of nano particle by carrying out chemical reaction between nano grain surface and treating agent, reach the purpose of surface modification; In addition, also can change the surface charge distribution of particle by dispersant adsorption, produce electrostatic stabilization and sterically hindered stabilization and strengthen dispersion effect.
1) coupling agent method
Coupling agent has the both sexes structure, a part of group in its molecule can with the various functional group reactionses of particle surface, form strong chemical bonding, some chemical reaction or physics can occur with organic polymer and be wound around in another part group.Particle after coupling agent treatment, both suppressed the reunion of particle itself, strengthened again the solubility of nano particle in organic media, can be dispersed in preferably in organic matrix, increased particles filled amount, thereby improve the combination property of goods, particularly tensile strength, impact strength, pliability and flexural strength.
2) esterification
Metal oxide is called esterification with the reaction of alcohol.With esterification, nano grain surface is modified, importantly made the surface of original hydrophilic oleophobic become the surface of oleophilic drainage, the modification of this function of surface is very important in actual applications.The esterification surface modification is that faintly acid is the most effective with neutral nano particle for surface.
3) spreading agent disperses
Select one or more suitable spreading agents to improve the dispersiveness of suspended matter, improve its stability and rheological.Spreading agent commonly used mainly contains the inorganic electrolyte of the surfactant (as long-chain fatty acid, cetyl trimethyl ammonium bromide (CTAB) etc.) that is comprised of lipophilic group and hydrophilic group, little relative molecular mass or inorganic polymer (as sodium silicate, sodium hexametaphosphate etc.), polymkeric substance and the polyelectrolyte (as gelatin, carboxymethyl cellulose, poly-methyl acrylate, polyethyleneimine etc.) of relative molecular mass greatly.But it should be noted that when the quantity not sufficient that adds people's spreading agent or when excessive, may cause flocculation.While therefore using spreading agent to disperse, must be controlled its consumption.
Interaction potential energy total between particle can be expressed as:
V
T＝V
WA+V
ER+V
SR
In formula, V
WAFor Van der Waals force potential energy; V
ERFor double electrode layer repulsion potential energy; V
SRScold potential energy for sterically hindered.
Hence one can see that, and the nanoparticulate dispersed stable mechanism mainly contains following three kinds:
1. electronic double layer repulsion theoretical (dlvo theory)
Dlvo theory is mainly to explain the mechanism that dispersed system is stable and affect the factor of stability by the electrostatic double layer theory of particle.This theory is can form an adsorbed layer at particle surface having ignored macromolecule, has also ignored because Polymer adsorption produces a kind of new repulsion simultaneously--set up in the situation of sterically hindered repulsion.This theory disclosed nano grain surface the relation of electrically charged and stability, the methods such as the pH value by reconciling solution or additional electrolytic solution, increase the particle surface electric charge, form electrostatic double layer, increase by Zeta potential, make between particle and produce electrostatic repulsion, realize the stable dispersion of particle.The stability of system is mainly can realize with the balance of Van der Waals force energy by electronic double layer repulsion, and expression formula is as follows
V
T＝V
WA+V
ER
In formula, V
TFor the total potential energy of two particle; V
WAFor Van der Waals force potential energy; V
ERFor double electrode layer repulsion potential energy.
2. sterically hindered stable mechanism
The electronic double layer repulsion theory can not be used for explaining the stability of the colloidal system of superpolymer or non-particle surface activating agent., for by adding the system of high molecular polymer as spreading agent, can explain with sterically hindered stable mechanism.High molecular polymer is adsorbed on the surface of nano particle; form one deck polymer protective film; surrounded nano particle; the lyophily group is stretched in water; and has a certain thickness; this shell has increased immediate distance between two particle, has reduced the interaction of Van der Waals force, thereby dispersed system is stablized.The particle that has adsorbed high molecular polymer will produce two kinds of situations when near each other: a kind of is that adsorbed layer is compressed and do not interpenetrate; Another kind is that adsorbed layer can interpenetrate, overlap each other.Both of these case all can cause maximum system energy to raise, and free energy increases.The first situation produces entropy repulsion potential energy because macromolecule loses structure entropy; The second situation, because overlapping region concentration raises, causes producing infiltration repulsion potential energy and mixes the repulsion potential energy.Thereby, if it will be very difficult having adsorbed that high molecular nano particle occurs to reunite again, thereby realized the dispersion of particle.
3. static steric hindrance stable mechanism
, if electrostatic stabilization and space steric effect are combined, can play better stablizing effect.The static steric stabilization, that nanoparticle surface has been adsorbed the charged stronger polymer molecule layer of one deck, charged polymer molecule layer both by itself with electrical charge rejection around particle, utilize again steric effect to prevent from doing the particle of Brownian movement close, produce the stable composition effect.Wherein the electrostatic charge source is mainly particle surface static charge, additional electrolyte and the high polyelectrolyte of anchoring group.Particle is when distant, and electrostatic double layer produces repulsion, and static is leading; Particle is when close together, and sterically hindered prevention particle is close.Spreading agent as the static steric dispersion generally has: polyacrylamide, sodium polyacrylate, sodium alginate, ammonium alginate, wooden sodium carbonate, petroleum sodium sulfonate, polyacrylic acid acyl ammonium, hydrolysis ammonium acrylate, phosphoric acid fat, ethoxy compound etc.
The dispersion of nano particle in medium is the process of a dispersion and flocculation balance., although physical method can better be realized the dispersion of nano particle in liquid phase medium,, in case external influence power stops,, due to the intermolecular force effect, can mutually assembling again between particle.And the employing chemical dispersion, by changing particle surface character, changes particle and liquid phase medium, particle and intergranular interaction, strengthens intergranular repulsive force, will produce the lasting effect that flocculation is reunited that suppresses.Therefore, in real process, physical dispersion and chemical dispersion should be combined, with the physical means solution, reunite, with chemical method, keep stably dispersing,, to reach better stably dispersing effect, obtain the strong inorganic nanoparticles compound polyimide film of corona resistance.
, along with the development of nano-dispersed technology, to the dispersion stabilization of nano particle in inorganic nanoparticles compound polyimide film raw material, more and more higher requirement will be proposed.How to judge the dispersion stabilization of nano particle in medium, just produced the appraisal procedure problem of dispersion stabilization.From the current study, mainly contain sedimentation, granularity observation method, Zeta potential method and light transmittance ratio method etc.
1) sedimentation
The poor system of dispersion stabilization is the rapid sedimentation of flocculation of a formula more, and the interface of precipitum and upper clear supernate formation one clear Zha, reaches very soon sedimentation equilibrium.The settling velocity that dispersion stabilization is good is slow, and the particle of dispersed system from top to bottom is the disperse of enrichment gradually and distributes, and there is no obvious sediment.The concrete operations of sedimentation are: scattered dispersed system poured in graduated cylinder, and standing, the volume of observation precipitum or height.
Sedimentation can be used for studying the impact of each factor on liquid dispersion system dispersion effect, can react truly the dispersion stabilization of nano particle in liquid medium, and easy and simple to handle, is present a kind of the most frequently used and the most reliable method.Weak point is that the test period is long, for the good dispersed system of dispersion stabilization, likely places 10d, sedimentation does not even occur half a year in one month.
2) granularity observation method
The granularity observation method is by the granularity of nano particle in the observation dispersed system or the appraisal procedure a kind of commonly used that particle diameter distributes.The dispersed system particle size that dispersion stabilization is good should be the size of a nano particle.Opposite granularity the greater, illustrate that this dispersed system has reunion to a certain degree on the one hand; It is affected by gravity greatlyr in dispersed system on the other hand, and settling velocity is accelerated, thereby has accelerated the instability of system.At present, the method for measuring the nanoparticle granularity is a lot, and the useful transmission Electronic Speculum is observed the dispersion effect of nano particle, and also useful special particle-size analyzer is observed, also useful X ray particle size analyzer the granularity of particle in the dispersed system.
Concrete operations from granularity observation method at present used, the granule size of measuring or size-grade distribution are all the results that observes after processing (as dilution) in dispersed system, as seen this method not only can not directly be measured outside the particle size of nano particle in liquid medium, and it is limited to take a sample, and result lacks statistical.
3) Zeta potential method
Nanoparticulate dispersed is in liquid medium, and particle surface, with the net charge of some, attracts the opposite charges of equivalent amount around it, and the current potential of fixed layer and diffusion layer intersection slipping plane is Zeta potential.The absolute value of Zeta potential is larger, and the electrostatic repulsion between particle is preponderated, and is difficult for reuniting, and illustrates that dispersed system is stable; On the contrary, the absolute value of Zeta potential is less, and the Van der Waals force between particle is preponderated, and easily reunites, and illustrates that the system dispersion stabilization is poor.Therefore, the method is exactly to assess the dispersion stabilization of dispersed system by the size of measuring the particle surface Zeta potential.By measuring the Zeta potential of particle surface, can reflect the stability of dispersed system,, to determine suitable electrolyte and system pH, finally obtain the good dispersed system of dispersion stabilization.
Assess the dispersion stabilization of dispersed system with the method for measuring Zeta potential, can draw soon test findings, this is the great advantage of the method.But the method is to set up on the theoretical foundation of electrostatic stabilization mechanism, and the dispersed system of inapplicable sterically hindered stabiliser system, have limitation.
4) light transmittance ratio method
The method is to utilize nano particle in dispersed system, to certain wavelength incident light, absorption is arranged, and the size of its absorbance meets Lambert-Beer's law, that is: A=-logT=ε
mBC
s.In formula, A is absorbance, ε
mFor molar absorptivity, b is the thickness of sample cell, C
sFor the content of nano particle in dispersed system, T is transmittance.At ε
m, under the identical condition of b, the content C of the negative logarithm of the transmittance of dispersed system and nano particle
sInversely proportional relation.Along with the increase of nano-particle content in dispersed system, transmittance reduces, and, if transmittance no longer reduces, can think that dispersed system has reached the state of stably dispersing.That is to say, for different dispersed systems, under the same conditions, the dispersion stabilization of the little person's system of transmittance will be got well.Generally with spectrophotometer, measure transmittance.
The advantage of the method is intuitively, saves time, but this method is a kind of appraisal procedure that puts forward according to Lambert-Beer's law, only is suitable for lean solution, and certain limitation is arranged, and is not the direct method of assessment dispersion stabilization equally.
Summary of the invention
The object of the present invention is to provide the dispersed detection method of a kind of inorganic nanoparticles compound polyimide film raw material, overcome the shortcoming of the dispersed detection method of existing inorganic nanoparticles.
1. sedimentation need to be poured scattered dispersed system in graduated cylinder into, and is standing, observes volume or the height of precipitum.Its test period is long, and the dispersed system that dispersion stabilization is good is likely placed sedimentation is not even occurred half a year in 10 days, one month.
2. the granularity observation method is granularity or the particle diameter distribution by nano particle in the observation dispersed system, the granule size that the method is measured or size-grade distribution are all the results that observes after processing (as dilution) in dispersed system, not only can not directly measure outside the particle size of nano particle in liquid medium, and it is limited to take a sample, and result lacks statistical.
3. the Zeta potential method is to set up on the theoretical foundation of electrostatic stabilization mechanism, and therefore the dispersed system of inapplicable sterically hindered stabiliser system also has limitation.
4. the transmittance rule puts forward according to Lambert-Beer's law, only is suitable for lean solution, and certain limitation is arranged, and is not the direct method of assessment dispersion stabilization equally.
The present invention, by measuring the voltage breakdown of inorganic nanoparticles compound polyimide film raw material, detects the dispersion stabilization of nano particle in inorganic nanoparticles compound polyimide film raw material; Obtain to have the inorganic nanoparticles compound polyimide film raw material of good dispersion with this,, in order to prepare the good inorganic nanoparticles compound polyimide film of corona-resistance property, met the requirement to the anti-high-frequency impulse of variable-frequency motor turn-to-turn insulation.
The present invention is by being achieved by following technical solution.
A kind of detection method of inorganic nanoparticles compound polyimide film raw material dispersiveness has following steps:
(1) get inorganic nano combined Kapton raw material to be measured and pour in inspection instrument, container is filled, and at the vacuum environment bubble removing that goes down, then put into the metal plate electrode in this sample;
(2) apply the 0-10kV alternating voltage to two-plate, by 0.5kV/s speed, from 0kV, start to increase voltage magnitude, until the inorganic nanoparticles compound polyimide film raw material discharge breakdown between pole plate records its voltage breakdown as the experiment detected value;
(3) the voltage breakdown detected value of step (2) and selected standard value are compared; This standard value is measured for by above-mentioned experimental technique, the good inorganic nanoparticles compound polyimide film raw material of dispersion of the polyimide raw material that do not add nano particle and standard being carried out standard test, repeatedly measure and average, with experimental results as standard value;
(4) Analysis of test results: detected value and standard value are more approaching, illustrate that in sample, nanoparticulate dispersed is more even, and inorganic nanoparticles compound polyimide film raw material dispersiveness is better.
During described step (3) standard value is determined, the good Kapton raw material of dispersion used is to determine that by scanning electron microscopy measurement its dispersiveness is good.
Advantage of the present invention and beneficial effect:
1. compare with sedimentation, detection method provided by the present invention need not to wait for the sedimentation of inorganic nanoparticles compound polyimide film raw material, can save time;
2. need not to inorganic nanoparticles compound polyimide film raw material process (as the dilution etc.), but the dispersiveness of direct-detection inorganic nanoparticles compound polyimide film raw material, result is accurate;
3. be not subjected to the restriction of various dispersion stabilization mechanisms;
4. be not subjected to the restriction of inorganic nanoparticles compound polyimide film raw material viscosity;
5. detect experimental facilities used simple, easy to operate, experimental result is directly perceived, accurate.
Description of drawings
Fig. 1 is the present invention's experiment device schematic diagram used;
Fig. 2 is the detection method process flow diagram of inorganic nanoparticles compound polyimide film raw material dispersiveness of the present invention.
Reference numeral of the present invention is as follows:
1---AC power 2---resistance
3---insulating carriage 4---lithographic plate electrode
5---inspection instrument 6---specimen
Embodiment
The invention will be further described below by specific embodiment.
The present invention is based on the shelf depreciation principle,, by measuring the voltage breakdown of inorganic nanoparticles compound polyimide film raw material, detect the dispersion stabilization of nano particle in inorganic nanoparticles compound polyimide film raw material.
Only have regional area to discharge in insulator, and run through, do not execute between alive conductor, this phenomenon is referred to as shelf depreciation.Shelf depreciation in the present invention occurs in the inside of insulator one inorganic nanoparticles compound polyimide film raw material, is inner shelf depreciation.Because inorganic nanoparticles compound polyimide film raw material consists of compound substance, the electric field intensity in different materials is different, and breakdown field strength is also different, and at first this just shelf depreciation may occur in certain material.If in inorganic nanoparticles compound polyimide film raw material, nanoparticulate dispersed is inhomogeneous, nano particle is reunited, the nano particle place of cohesion tends at first occur shelf depreciation, finally causes inorganic nanoparticles compound polyimide film raw material to puncture.
The breakdown voltage value that detects the gained sample is lower, illustrates that this inorganic nanoparticles compound polyimide film raw material dispersiveness is poorer; The voltage breakdown of detection gained sample is the value of being near the mark more, illustrates that this inorganic nanoparticles compound polyimide film raw material dispersiveness is better.
Utilization of the present invention pick-up unit as shown in Figure 1, the upper end of inspection instrument 5 is provided with insulating carriage 3, is fixed with two lithographic plate electrodes 4 above insulating carriage 3, has a lithographic plate electrode to be connected with resistance 2, the other end of resistance 2 connects high-voltage ac power, the direct ground connection of another lithographic plate electrode; During test, sample is filled inspection instrument 5.
Detection method of the present invention as shown in Figure 2.
Embodiment 1 (the voltage tester sample settles the standard)
(1) prepare nano combined Kapton in laboratory.In preparation process, nano particle processes to improve its dispersiveness through surface conditioning agent, adopts ultrasonic and mechanical blending method in the nano particle dispersion process, fully the dispersing nanometer particle.Inorganic nano/the polyamic acid solution that makes is divided into two parts, finished film is made in a plastic film mulch imidization, and finished product is confirmed its dispersiveness by the scanning electron microscope imaging, favorable dispersibility is got another part inorganic nano/polyamic acid solution as the normal voltage test sample book.
(2) Kapton raw material to be measured is poured in the diagram pick-up unit, container is filled, and at the vacuum environment bubble removing that goes down, then put into the metal plate electrode in this sample;
(3) press the circuit of connection shown in schematic diagram, to two-plate, apply the 0-10kV alternating voltage, press 0.5kV/s speed and increase voltage magnitude, until the Kapton raw material discharge breakdown between pole plate, record voltage breakdown this moment is 4.1kV;
(4) repeat above-mentioned steps four times, and to record respectively breakdown voltage value be 4.0kV, 4.3kV, 4.1kV, 4.2kV.Above-mentioned five mean value results are 4.14kV, with this magnitude of voltage as a standard value.
(1) laboratory prepares nano combined Kapton, and in preparation process, nanoparticle surface is untreated, and adopts pure mechanical dispersion process to disperse nano particle, the nano combined Kapton raw material that makes is got quantitative as detecting sample.Method is same as embodiment 1, and standard value is the 4.14kV of embodiment 1.
(2) Kapton raw material to be measured is poured in the diagram pick-up unit, container is filled, and at the vacuum environment bubble removing that goes down, then put into the metal plate electrode in this sample;
(3) press the circuit of connection shown in schematic diagram, to two-plate, apply the 0-10kV alternating voltage, press 0.5kV/s speed and increase voltage magnitude, until the Kapton raw material discharge breakdown between pole plate, record voltage breakdown this moment is 3.1kV;
(4) the voltage breakdown detected value of step (3) and the standard value 4.14kV of step 1 are compared, find its breakdown voltage value lower than standard value, difference, greater than 20%, assert that this sample dispersiveness is poor.
(1) get actual industrial production Nanoparticles During compound polyimide film raw material as testing cost.Standard value is still the 4.14kV of embodiment 1.
(2) Kapton raw material to be measured is poured in the diagram pick-up unit, container is filled, and at the vacuum environment bubble removing that goes down, then put into the metal plate electrode in this sample;
(3) press the circuit of connection shown in schematic diagram, to two-plate, apply the 0-10kV alternating voltage, press 0.5kV/s speed and increase voltage magnitude, until the Kapton raw material discharge breakdown between pole plate, record voltage breakdown this moment is 4.0kV;
(4) the voltage breakdown detected value of step (3) and the standard value 4.14kV of step 1 are compared, find close to standard value, difference within 5%, is assert this sample favorable dispersibility.
The present invention is mainly in the electric insulation technical field.
Claims (2)
1. the detection method of an inorganic nanoparticles compound polyimide film raw material dispersiveness has following steps:
⑴ get inorganic nanoparticles compound polyimide film raw material to be measured and pour in inspection instrument, container is filled, and at the vacuum environment bubble removing that goes down, then put into the metal plate electrode in this sample;
⑵ apply the 0-10kV alternating voltage to two-plate, by 0.5kV/s speed, from 0kV, starts to increase voltage magnitude, until the inorganic nanoparticles compound polyimide film raw material discharge breakdown between pole plate records its voltage breakdown as the experiment detected value;
⑶ compare the voltage breakdown detected value of step ⑵ and selected standard value; This standard value is measured for by above-mentioned experimental technique, the good inorganic nanoparticles compound polyimide film raw material of dispersion of the polyimide raw material that do not add nano particle and standard being carried out standard test, repeatedly measure and average, with experimental results as standard value;
⑷ Analysis of test results: detected value and standard value are more approaching, illustrate that in sample, nanoparticulate dispersed is more even, and inorganic nanoparticles compound polyimide film raw material dispersiveness is better.
2. according to claim 1 a kind of detection method of inorganic nanoparticles compound polyimide film raw material dispersiveness, it is characterized in that, during described step ⑶ standard value is determined, the good inorganic nanoparticles compound polyimide film raw material of dispersion used is to determine that by scanning electron microscopy measurement its dispersiveness is good.
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