Hierarchically Multifunctional Polyimide Composite Films with Strongly Enhanced Thermal Conductivity

The development of lightweight and integration for electronics requires flexible films with high thermal conductivity and electromagnetic interference(EMI) shielding to overcome heat accumulation and electromagnetic radiation pollution.Herein,the hierarchical design and assembly strategy was adopted to fabricate hierarchically multifunctional polyimide composite films,with graphene oxide/expanded graphite(GO/EG) as the top thermally conductive and EMI shielding layer,Fe_(3)O_(4)/polyimide(Fe_(3)O_(4)/PI) as the middle EMI shielding enhancement layer and electrospun PI fibers as the substrate layer for mechanical improvement.PI composite films with 61.0 wt% of GO/EG and 23.8 wt% of Fe_(3)O_(4)/PI exhibits high in-plane thermal conductivity coefficient(95.40 W(m K)^(-1)),excellent EMI shielding effectiveness(34.0 dB),good tensile strength(93.6 MPa) and fast electric-heating response(5 s).The test in the central processing unit verifies PI composite films present broad application prospects in electronics fields.

PREPARATION OF POLYIMIDE-BaTiO3 HYBRID FILMS BY A DISPERSION PROCESS AND THEIR MICROSTRUCTURE

Barium titanate (BaTiO3) powders with particle sizes of 30 similar to 50 nm were prepared from barium stearate, titanium alkoxides and stearic acid by stearic acid-gel method. Dispersing the agglomerate of BaTiO3 nanoparticles into poly(amic acid) solution followed by curing led to the formation of polyimide hybrid films. The hybrid films were transparent and well distributed with BaTiO3 nanoparticles when the BaTiO3 content was less than 1 wt%. Highly loaded hybrid film containing 30 wit % BaTiO3 was tough, had a smooth surface and possessed much higher dielectric and piezoelectric constants than the parent polyimide.

Influence of Curing Accelerators on the Imidization of Polyamic Acids and Properties of Polyimide Films

In order to lower the imidization temperature of polyamic acids（PAA）, the catalytic activities of the curing agents p-hydroxybenzoic acid（PHA）, quinoline（QL）, benzimidazole（BI）, benzotriazole（BTA）, triethylamine（Et_3N） and 1, 8-diazabicyclo [5.4.0]undec-7-ene（DBU） were investigated in the process of thermal imidization of PAA. In addition, the effect of these various curing agents on the thermal stabilities and mechanical properties of the resultant polyimide（PI） films was determined. Quinoline was found to be an effective curing accelerator in the use of two-step method for synthesizing PI. Due to its moderate base strength, low steric crowding effect and moderate boiling point, quinoline could not only accelerate PAA to achieve imidization completely at 180 ℃, but also maintain the mechanical properties and thermal stability of the ordinary PI film. Any residual quinoline could be removed from PI films by heating at 250 ℃ for 4 h.

Silicone-coated polyimide films deposited by surface dielectric barrier discharges

Hybrid dielectric barrier discharges are investigated for plasma generated on the surface of a dielectric layer, where two conducting electrodes of high voltage and ground are formulated on the upper and bottom surfaces. Using a flexible thin polyimide-film of a thickness ranging from 25 to 125 μm, a plasma is generated with a voltage of about 1 kV and a frequency of 40 kHz.However, the surface of the dielectric layer was etched through a chemical reaction involving plasma oxygen radical species, and thus the polyimide films failed readily, resulting in dielectric breakdown within short operating time ranging from a few minutes to several tens of minutes,based on the film thicknesses of 25 μm and 125 μm, respectively. These plasma erosions were prevented by coating the polyimide surface with a 25 μm thick silicone paste. The siliconecoated film surface was then reinforced remarkably against plasma erosion as the organic polymer was vulnerable to chemical reaction of the plasma species, while the inorganic silicone exhibited a high chemical resistance against plasma erosion.

EFFECT OF MONTMORILLONITE ADDITION ON MECHANICAL CHARACTERIZATIONS OF POLYIMIDE NANOCOMPOSITE FILMS

Tensile deformation and fracture characteristics of polyimide/montmorillonite nanocomposite films are investigated to enhance the particular mechanical properties and understand the effective factors in dominating the mechanical properties of nanocomposites, such as the nanolayer, matrix and nanolayer/matrix interface. How to contribute to the mechanical properties of nanocomposite film is a very complex problem. In this paper, these factors are analyzed based on the addition amount and fracture mechanics. The results indicate that the specimen at 20 wt% MMT breaks prematurely with a fracture strength （σb = 78 MPa） much lower than that （σb = 128 MPa） at the 1 wt% MMT. However, the Young＇s modulus （3.2 GPa） of the former is higher than that （1.9 GPa） of the latter. Fractography also indicates that the brittle cracking formed in high content addition is the main cause of failure but microscopically ductile fracture morphology still exists locally. And for the trace element addition, the smaller threading slipping veins are evenly distributed on the entire fracture section of these films. Therefore, these characteristics would presumably be associated with both the concentration effects of size of nanocomposite sheets and the increasing deformation harmony in nanolayers.

Formation and Characterization of Pd,Pt and Pd-Pt Alloy Films on Polyimide by Catalyst-Enhanced Chemical Vapor Deposition

Platinum, palladium and their alloy films on polyimide were formed by catalyst-enhanced chemical vapor deposition （CVD） in the carrier gas （N2, O2） at 220-300℃ under reduced pressure and normal pressure. The deposition of palladium complexes [ Pd（（η3-allyl）（hfac） and Pd（hfac）2 ] gives pure palladium film, while the deposition of platinum needs the enhancement of palladium complex by mixing precursor platinum complex Pt（COD）Me2 and palladium complex in the same chamber. The co-deposition of Pd and Pt metals was used for the deposition of alloy films. During the CVD of palladium-platinum alloy, the Pd/Pt atomic ratios vary under different co-deposition conditions. These metal films were characterized by XPS and SEM, and show a good adhesive property.

COMPENSATION EFFECT OF POLYIMIDE THIN FILMS ON NORMALLY WHITE TWISTED NEMATIC LIQUID CRYSTAL DISPLAYS

The disadvantages of Normally White Twisted Nematic Liquid Crystal Display (NW-TN-LCD) were discussed. The reason that the negative birefringent polyimide thin films were used to compensate NW-TN-LCD to decrease off-axis leakage, improve contrast ratios and enlarge viewing angles was explained in this paper. A certain polyimide thin film was taken as an example to show compensation effect on NW-TN-LCD.

Research of Trap and Electron Density Distributions in the Interface of Polyimide/Al2O3 Nanocomposite Films Based on IDC and SAXS

The distributions of traps and electron density in the interfaces between polyimide （PI） matrix and Al2O3 nanoparticles are researched using the isothermal decay current and the small-angle x-ray scattering （SAXS） tests. According to the electron density distribution for quasi two-phase mixture doped by spherical nanoparticles, the electron densities in the interfaces of PI/Al2O3 nanocomposite films are evaluated. The trap level density and carrier mobility in the interface are studied. The experimental results show that the distribution and the change rate of the electron density in the three layers of interface are different, indicating different trap distributions in the interface layers. There is a maximum trap level density in the second layer, where the maximum trap level density for the nanocomposite film doped by 25 wt% is 1.054 × 10^22 eV·m^-3 at 1.324eV, resulting in the carrier mobility reducing. In addition, both the thickness and the electron density of the nanocomposite film interface increase with the addition of the doped Al2O3 contents. Through the study on the trap level distribution in the interface, it is possible to further analyze the insulation mechanism and to improve the performance of nano-dielectric materials.

Microscopic degradation mechanism of polyimide film caused by surface discharge under bipolar continuous square impulse voltage

Polyimide （PI） film is an important type of insulating material used in inverter-fed motors. Partial discharge （PD） under a sequence of high-frequency square impulses is one of the key factors that lead to premature failures in insulation systems of inverter-fed motors. In order to explore the damage mechanism of PI film caused by discharge, an aging system of surface discharge under bipolar continuous square impulse voltage （BCSIV） is designed based on the ASTM 2275 01 standard and the electrical aging tests of PI film samples are performed above the partial discharge inception voltage （PDIV）. The chemical bonds of PI polymer chains are analyzed through Fourier transform infrared spectroscopy （FTIR） and the dielectric properties of unaged and aged PI samples are investigated by LCR testers HIOKI 3532-50. Finally, the micro-morphology and micro-structure changes of PI film samples are observed through scanning electron microscopy （SEM）. The results show that the physical and chemical effects of discharge cut off the chemical bonds of PI polymer chains. The fractures of ether bond （C-O-C） and imide ring （C-N-C） on the backbone of a PI polymer chain leads to the decrease of molecular weight, which results in the degradation of PI polymers and the generation of new chemical groups and materials, like carboxylic acid, ketone, aldehydes, etc. The variation of microscopic structure of PI polymers can change the orientation ability of polarizable units when the samples are under an AC electric field, which would cause the dielectric constant e to increase and dielectric loss tan ~ to decrease. The SEM images show that the degradation path of PI film is initiated from the surface and then gradually extends to the interior with continuous aging. The injection charge could result in the PI macromolecular chain degradation and increase the trap density in the PI oolvmer bulk.

Preparation and Properties of Copper Fine Wire on Polyimide Film in Air by Laser Irradiation and Mixed-Copper-Complex Solution Containing Glyoxylic Acid Copper Complex and Methylamine Copper Complex

Formation of copper wiring on a polyimide film by laser irradiation to a stable copper-complex film consisting of glyoxylic acid copper complex and methylamine copper complex in air has been investigated. A stable metallic copper on the polyimide film was precipitated even in air. Since this copper was generated only in the laser-irradiated parts, direct patterning of copper wiring was possible. It was also found that copper was precipitated by electroless copper plating on the laser-deposited copper wiring and it was possible to thicken the copper wiring by this precipitation. The resistivity of the copper wiring was almost the same as that of the bulk of metallic copper. The developed method—combining laser irradiation to a copper-complex-coated film and electroless copper plating—enables the high-speed deposition of fine copper wiring on a polyimide film in air by a printing process, indicating an inexpensive and useful process for fabricating copper wiring without high vacuum facility and heat-treatment under inert gas.

Degradation Mechanism of Polyimide Film Under Square Impulse Voltages

Partial discharge (PD) under a sequence of high-repetition-rate square pulses is one of the key factors leading to premature failure of insulation systems of inverter-fed motors. Polyimide (PI) film is an important type of insulating material used in the inverter-fed motors. In this paper, micro-morphology and structure change of PI film aged by bipolar continuous square impulse voltage (BCSIV) with ampli- tude above partial discharge inception voltage (PDIV) are investigated by scanning electron microscope (SEM). The chemical bonds of PI chain are analyzed through Fourier transform infrared spectroscopy (FTIR). The results show that the degradation mechanism of PI film is the fracturing of chemical bonds caused by the erosion from PDs. Three layers are displayed in both 100 HN film and 100 CR film. The de- gradation path of PI film is initiated from surface and then gradually extends to the interior with continuous aging. Nano-fillers can retard the degradation of PI film and prolong its lifetime.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

Preparation and Gas Barrier Characteristics of Polysilazane-Derived Silica Thin Films Using Ultraviolet Irradiation

The gas barrier film formation technique using simultaneous photo-irradiation and heat-treatment has been researched on alicyclic polyimide film coated with a polysilazane solution. A fine SiO2 thin film on polyimide film was formed at low temperatures, which greatly improved the substrate’s gas barrier characteristics by this technique. The values of gas barrier characteristics depended on the substrate temperature at the time of photo-irradiation. For photo-irradiated thin film heat-treated to 150°C, the water vapor transmission rate and oxygen transmission rate fell below the equipment measurement limit of 0.02 g/m2/day and 0.02 cm3/m2/day, respectively. This polyimide film with a gas-barrier film coating has good transmittance in the region of visible light, heat resistance, and flexibility.

A 3D graphene/polyimide fiber framework with improved thermal conductivity and mechanical performance

The integration of electronic components and the popularity of flexible devices have come up with higher expectations for the heat dissipation capability and comprehensive mechanical performance of thermal management materials.In this work,after the modification of polyimide(PI)fibers through oxidation and amination,the obtained PDA@OPI fibers(polydopamine(PDA)-modified pre-oxidized PI fibers)with abundant amino groups were mixed into graphene oxide(GO)to form uniform GO-PDA@OPI composites.Followed by evaporation,carbonization,graphitization and mechanical compaction,the G-gPDA@OPI films with a stable three-dimensional(3D)long-range interconnected covalent structure were built.In particular,due to the rich covalent bonds between GO layers and PDI@OPI fibers,the enhanced synergistic graphitization promotes an ordered graphitized structure with less interlayer distance between adjacent graphene sheets in composite film.As a result,the optimized G-gPDA@OPI film displays an improved tensile strength of 78.5 MPa,tensile strain of 19.4%and thermal conductivity of 1028 W/(m·K).Simultaneously,it also shows superior flexibility and high resilience.This work provides an easily-controlled and relatively low-cost route for fabricating multifunctional graphene heat dissipation films.

A Novel Diamine,4'-Phenyiphenyi 4-(3",5"-Diaminobenzoyioxy)-benzoate and Longer Side-chain Polyimide

This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.

Synthesis of a Novel Diamine 4-[(4'-Butoxyphenoxy)carbonyl]phenyl-3",5"-diaminobenzoate and Corresponding Polyimides

A novel diamine 4-[（4＇-butoxyphenoxy）carbonyl]phenyl-3＂,5＂-diaminobenzoate （BCDA） was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4＇-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature, solubility and the pretilt angles, were carded out.

Polyimide Humidity Integrated Sensor Fabricated Using the MEMS Process

This paper reports on the fabrication and sensing characteristics of Polyimide-based humidity sensor,based on that,a new integrated circuit of humidity measurement has been designed.It is a novel capacitive-type systems on a chip structure using the MEMS process.The results show that the new sensor presents sensing characteristics over a humidity range from 10%～70% RH at 20℃,and the sensor is able to fabricated together with ICs technology.The result shows that integration of humidity sensor with integrated circuit of humidity measurement is considerably easier when they are built in sensing groove.The appeal of a new structure like this brings the possibility of applications that would require the flexibility of simple screen printing.

NOVEL POLYMER WIDE VIEWING ANGLE COMPENSATION FILMS FOR LIQUID CRYSTAL DISPLAYS(LCDS)

We report on generating uniaxial negative birefringent compensation films, made of specifically designedpolyimides. These polymers were synthesized via a polycondensation of dianhydride [such as 2, 2' -bis(3, 4-dicarboxyphenyl)hexafluoropropane dianhydride] and 2, 2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. The uniaxial negative birefringent (n_x =n_y > n_z) polyimide substrates are achieved using a solution-casting method in conventional solvents, which exhibit thedesirable optical phase retardation [(n_x - n_z)×d] values from 50 to 400 nm varying with the film thickness. In thesepolyimide films, the long chain rigid molecules adopt intrinsic planar orientaion. In detail, the majority of phenylene-imiderings and phenylenes preferentially adopt nearly planar conformations parallel to the film substrae. In addition, these filmsalso possess high transparency (or transmittance) and little color shift. The unique color dispersion curve indicates that thistype of materials is very suitable for the applications in LCDs due to an excellent mimic for the retardation color dispersioncurve with respect to LC molecules. Significantly low in-plane retardation (< 1 nm) allows this new technology based film toachieve sufficiently high contrast ratio while highly negative retardation dramatically suppresses the gray scale inversion toimprove the viewing angle performance in a variety of new mode LCDs.

Synthesis and Properties of a Novel Polyimide with Side Chain Containing Biphenyl Unit

A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide（PI） films with different side chain contents was synthesized from biphenyltetracarboxylicdianhydride（BPDA）,4,4＇-oxydianiline（ODA） and C6BBC4,and their thermal properties,optical transparency and liquid crystal alignment property,and so on,were investigated by thermogravimetric analysis（TGA）,differential scanning calorimetry（DSC）,crystal rotation method,polarizing microscopy and UV-Vis spectra.With the content of side chained diamine increasing from 0 to 100%,the η inh of poly（amide acid）（PAA） decreased rapidly from 3.0 to 0.51,the glass transition temperature（T g） of polyimides（PIs） decreased from 274 ℃ to 203 ℃ and the Vis-light transmittance of alignment films substantially increased.As for the alignment properties,the pretilt angle of PI alignment films without rubbing could reach 90° when the content of C6BBC4 was 60% or more.At the same time,the alignment stability could meet the industrial requirements.It was considered that the alkoxy spacer,the biphenyl unit and the alkoxy tail may all play important roles in achieving a large pretilt angle even up to 90°,and the introduction of only the alkoxy spacer or alkoxy tail can also improve the pretilt angle,but not by much.

Coefficient of thermal expansion of stressed thin films

A new technique was proposed to determine the coefficient of thermal expansion (CTE) of thin films at low temperature. Different pre-stress could be applied and the elastic modulus of materials at different temperatures was measured with CTE simultaneously to eliminate the influence of mechanical deformation caused by the pre-stress. By using this technique, the CTEs of polyimide/silica nanocomposite films with different silica doping levels were experimentally studied at temperature from 77 K to 287 K, and some characteristics related to this new technique were discussed.