Colorless Films Research Articles

Crosslinked Colorless Polyimide Films via Oxazole Groups as Crosslinking Agent: Preparation and Properties

Crosslinked Colorless Polyimide Films via Oxazole Groups as Crosslinking Agent: Preparation and Properties

Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.

Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.

Study of the effect of Adding Green Tea (Camellia sinensis) Extract on the Propoerties of Biodegradable Film from κ-Carrageenan

Carrageenan is a polysaccharide widely used as a material in the packaging industry in search of plastic replacement. κ-Carrageenan contains the lowest amount of sulfat group among other types of carrageenan which makes it the most hydrophobic one. Hence, the most suitable kind for this particular purpose. This research combined commercially available of both κ-Carrageenan and green tea extract (gte) to create a biodegradable film and then to study its characteristics. The concentration of gte was made as 0 µg/mL, 5 µg/mL, and 1 µg/mL while the concentration of κ-Carrageenan and glycerol remained constant. Incorporation of gte produces in darker, colorless film. While there is no effect of gte addition in water content observed, the higher concentration of gte will create a thinner film and lower level of water vapor permeability (WVP). An additional study of the mechanical properties of κ-Carrageenan/gte film indicated a direct proportion between the concentration of gte and tensile strength of the film. Meanwhile, there is no sign of correlation between gte concentration and elongation at break. SEM study displayed a more compact surface with smaller pores when the concentration of gte is increased

Development of electroconductive colorless films using printing technology toward flexible electronics

Development of electroconductive colorless films using printing technology toward flexible electronics

Aromatic Poly(dithioacetal)s: Spanning Degradability, Thermostability, and High Refractive Index Towards Eco-friendly Optics.

In the quest for eco-friendly optics, high refractive index polymers (HRIPs) with degradability have been one of the desirable optical materials for realizing eco-friendly and efficient lighting technologies. However, it has been challenging for HRIPs to simultaneously realize thermostability, high refractive index (RI), visible transparency, and efficient degradability, all of which are essential for their practical use. In this context, we herein focus on aromatic poly(dithioacetal)s, composed of visible-transparent yet degradable dithioacetal moieties and rigid diphenyl disulfide spacers, exhibiting moderately high Tg (> 60 °C), high RI (> 1.7), and colorless film features. In addition, poly(dithioacetal)s can balance (1) high stability under the operating conditions even upon heating and (2) quantitative degradability that can selectively yield cyclic low-molecular-weight products that can be further repolymerized upon further addition of an acid catalyst. These results provide a key concept for high refractive index polymers that allow on-demand degradability and recyclability without compromising their high potential thermal and optical properties.

Mechanically Robust and Colorless Polyimide Films Cross-Linked with a Cycloaliphatic Amide Linkage

Mechanically Robust and Colorless Polyimide Films Cross-Linked with a Cycloaliphatic Amide Linkage

Effect of methyl trifluoride substitution on colorless transparency of polyimide: A DFT/TD-DFT study

The rapid advancement of flexible electronic devices has rendered high-performance colorless transparency polyimide (PI) films essential for energy storage and devices. However, there still remains controversy regarding the charge-transfer complexes in relation to the optical properties of PIs. Herein, we employed a combination of DFT and TD-DFT methods to elucidate the hole and electron characteristics of PIs. The results revealed that the incorporation of a CF3 group significantly enhances the dipole moment. Notably, the incorporation of CF3 groups onto both the anhydride and diamine units impedes charge transfer, resulting in a reduction of the HOMO energy level and an increse of the LUMO energy. The calculation results also indicate that the introduction of CF3 groups markedly hinders charge transfer within P4 in its excited state, leading to the minimum values for three characteristic parameters (D = 2.60 Å, CT = 0.51 e, t = 0.53 Å). Therefore, P4 exhibits a shortest charge transfer pathway resulting in minimal electron transfer and obvious blue-shifted UV–vis spectra, thus contributing to its excellent colorless transparency. This work provides a theoretical foundation and guidance for targeted design and development of colorless transparent PI films.

Ultraviolet-to-Blue Light Conversion Film Affects Both Leaf Photosynthetic Traits and Fruit Bioactive Compound Accumulation in Fragaria × ananassa

The influence of light downconversion films (red, pink and blue films) on leaf physiological features and fruit bioactive compound accumulation was studied in strawberry plants. Red, pink and blue films were able to convert light less utilised by plants into more efficient light wavebands with various possibilities depending on the film characteristics (blue film shifts UV into blue radiation; red film shifts green into red radiation, pink film shifts UV and green into blue and red radiation but to a lesser extent than red film). Indeed, by enhancing the quality of light available for photosynthesis, the utilization of these films holds the potential to improve agricultural productivity and sustainability. All of these light downconversion films resulted in higher plant fresh weight compared to a control colourless (Cnt) film, with plants grown under blue film (UV-to-blue light conversion) showing the most impressive results in terms of total leaf area (+25%), leaf thickness (+10%) and leaf mass per area (+15%). Simultaneously, during the flowering stage, plants under blue film had a higher net photosynthetic rate due to the increase in photosynthetically efficient wavelengths. Moreover, blue film resulted in the highest total phenolic (+40% and +28% than red and pink films, respectively) and flavonoid content (+54%, +84%, +70% than Cnt, red and pink films, respectively) in fruit, with specific effects on targeted phenols, i.e., quercetin, ellagic acid and its glycoside, ellagitannins, and procyanidins. In conclusion, the use of the UV-to-blue conversion light film tested herein represents an innovative solution to increase strawberry yield and promote fruit nutraceutical features, playing a pivotal role in ensuring food quality and security and sustainable agricultural practices.

Tuning Spatially Resolved Shape Memory Effects of Stimuli‐Responsive Macroporous Photonic Crystals

Stimuli‐responsive photonic crystals with patterned microstructures are of great interest in developing reconfigurable nano‐optical devices. Leveraging unconventional all‐room‐temperature shape memory efforts and spatially resolved photopolymerization, herein, a facile method for micropatterning stimuli‐responsive photonic crystals is reported. Macroporous shape memory polymer (SMP) photonic crystals fabricated by colloidal templating can be deformed by cold programming, triggering the disappearance of their original structural colors. Exposure of the deformed samples to UV light through a photomask selectively disables the shape memory capabilities in the UV‐exposed regions. Hidden micropatterns defined by the photomask can be revealed by exposing the colorless SMP films to ethanol vapor, which triggers the shape memory recovery of the “memorized” ordered microstructures and the corresponding structural colors. Extensive nanoindentation experiments indicate that the exposure to UV light increases the crosslinking density and enhances the elastic modulus and toughness of the exposed regions by a factor of ≈2.0 and ≈5.2, respectively. Due to the formation of these extra crosslinks in the deformed configuration, they prevent normal shape memory behavior where the strained polymer chains rearrange from the temporary to permanent configuration when triggered by an external stimulus. This simple micropatterning technology can enable multistimuli‐responsive reconfigurable nanophotonic devices and chromogenic anticounterfeiting labels.

Heat-sealable, transparent, and degradable arabinogalactan/polyvinyl alcohol films with UV-shielding, antibacterial, and antioxidant properties

Petroleum-based packaging materials are nondegradable and unsustainable and thus are harmful to the environment. Renewable packaging films prepared from bio-based raw materials are promising alternatives to petroleum-based packaging materials. In this study, colorless and transparent bio-based films were successfully cast using a solution containing a mixture of arabinogalactan (AG) and poly (vinyl alcohol) (PVA). Vanillin was incorporated into the mixture to endow the films with UV-shielding, antioxidant, and antibacterial properties. The morphological, physical, antioxidant, and antibacterial properties of the blend films were then characterized. At an AG:PVA weight ratio of 1:3, and the vanillin content was 0.15 %, the tensile strength of the AG/PVA/Vanillin (APV) films reached ~28 MPa, while their elongation at break reached ~475 %. The addition of vanillin significantly affected the antioxidant and antibacterial properties of the blend films, which exhibited superb UV barrier capacity. The APV films exhibited extremely low oxygen transmittance, delaying the onset of mold/rot in strawberries and reducing their weight loss. Because of the heat sealability of the blend films, they can be used for encapsulating various substances, such as concentrated laundry liquid. Moreover, the blend films were recyclable and biodegradable. Thus, these films have great potential for applications that require sustainable packaging.

Revealing the ESIPT process in benzoxazole fluorophores within polymeric matrices through theory and experiment.

The impact of the polymeric matrix on the photophysical characteristics of monomeric dyes responsive to excited-state intramolecular proton transfer (ESIPT) was investigated through UV-Vis absorption as well as steady-state and time-resolved emission spectroscopies. For this purpose, two benzoxazole monomers (M1 and M2) with acryloyl groups at different positions in their molecular structures were employed to facilitate covalent bonding within a styrene chain. Our findings reveal significant variations in their excited-state properties due to the proximity of the acryloyl groups, which affects the energy barrier of the ESIPT reaction, the emission wavelength, and the balance between the normal and tautomeric forms. The experimental results were corroborated through theoretical investigations at the DFT/TDDFT level, specifically using the B3LYP-D3/def2-TZVP methodology. Three notable observations emerged: donor/acceptor groups at the meta/para positions induced electron distribution changes, causing red-shifted emission for M2; in the polymer film, particularly in PM1, intramolecular hydrogen bond deactivation favored N* emission over T* emission; and the zwitterionic character of the T* species. This study underscores the advantages of functionalization in polymers, which can lead to colorless films and prevalent N* or T* emission, and contributes valuable insights into molecular design strategies for tailoring the photophysical properties of polymeric materials.

Anti-UV Passive Radiative Cooling Chiral Nematic Liquid Crystal Films for Thermal Management.

Passive radiative cooling (PRC) can spontaneously dissipate heat to outer space through atmospheric transparent windows, providing a promising path to meet sustainable development goals. However, achieving simultaneously high transparency, color-customizable, and thermal management of PRC anti ultraviolet (anti-UV) films remains a challenge. Herein, a simple strategy is proposed to utilize liquid crystalline polymer, with high mid-infrared emissive, forming customizable structural color film by molecular self-assembly and polymerization-induced pitch gradient, which guarantees the balance of transparency in visible spectrum and sunlight reflection, rendering anti-UV colored window for thermal management. By performing tests, temperature fall of 5.4 and 7.9°C are demonstrated at noon with solar intensity of 717Wm-2 and night, respectively. Vivid red-, green-, blue-structured colors, and colorless films are designed and implemented to suppress the solar input and control the effective visible light transmissivity considering the efficiency function of human vision. In addition, temperature rise of 11.1°C is achieved by applying an alternating current field on the PRC film. This study provides a new perspective on the thermal management and aesthetic functionalities of smart windows and wearables.

Colorless and transparent polyimide nanocomposites using organically modified montmorillonite and mica

In this study, we introduce a method for replacing the glass used in existing display electronic materials, lighting, and solar cells by synthesizing a colorless and transparent polyimide (CPI) film with excellent mechanical properties and thermal stability using a combination of new monomers. Poly(amic acid) (PAA) was synthesized using dianhydride 4,4′-biphthalic anhydride (BPA) and diamine 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (AHP). Various contents of organically modified montmorillonite (MMT) and mica were dispersed in PAA solution through solution intercalation, and then CPI hybrid films were prepared through multi-step thermal imidization. The organoclays synthesized to prepare CPI hybrid films were Cloisite 93A (CS-MMT) and hexadimethrine-mica (HM-Mica) based on MMT and mica, respectively. In particular, the diamine monomer AHP containing a –OH group was selected to increase the dispersibility and compatibility between the hydrophilic clays and the CPI matrix. To demonstrate the characteristics of CPI, the overall polymer structure was bent and a strong electron withdrawing –CF3 group was used as a substituent. The thermomechanical properties, morphology of clay dispersion, and optical transparency of the CPI hybrid films were investigated and compared according to the type and content of organoclays. Two types of organoclays, CS-MMT and HM-Mica, were dispersed in a CPI matrix at 1 to 7 wt%, respectively. In electron microscopy, most of the clays were uniformly dispersed in a plate-like shape of less than 20 nm at a certain critical content of the two types of organoclays, but agglomeration of the clays was observed when the content was higher than the critical content. Hybrids using HM-Mica had better thermomechanical properties and hybrids containing CS-MMT had better optical transparency.

Synthesis and characterization of high Tg and colorless polyamide-imide films derived from amide-containing diamines with different trifluoromethyl substitution

Four new diamines (3TFDABA, 2TFDABA, 22TFDABA and TFAPTA) were successfully synthesized to investigate the effect of different trifluoromethyl (CF3) substitution position on poly(amide-imide)s (PAIs) properties. High-performance PAIs were prepared from high-temperature polycondensation of these diamines with 6FDA dianhydride. All the PAI films exhibited good heat resistance with glass-transition temperatures (Tgs) of 311–392 °C, good 5% weight loss temperatures (Td5%s) of 480–510 °C in nitrogen, and excellent optical transparency with T450 ranging from 52% to 84%. According to the monomer structural design, a high heat resistant and colorless poly(amide-imide) film (PAI-2-6FDA), with excellent optical properties (T450 of 82%), outstanding thermal properties (Td5% of 499 °C and Tg of 392 °C), and good mechanical properties (tensile strength of 123 MPa, tensile modulus of 4.4 GPa) was achieved. A comprehensive structure-to-property relationship study revealed that the CF3 in ortho-position of the amino group effectively inhibited the rotation between imide ring and benzene, thus improved the heat resistance of the film. Moreover, it could also weaken the generation of charge transfer complexes through strong electron-withdrawing ability, which is beneficial for the synthesis of colorless polyimides.

Thiol‐ene polymerization of double‐decker‐shaped phenyl‐substituted silsesquioxanes and thiol monomers

AbstractPolymers incorporating double‐decker‐shaped phenyl‐substituted silsesquioxane (DDSQ) into the main chain are expected to exhibit excellent thermal stability and significantly reduced dynamics of the polymer segments. In this study, thiol‐ene polymerization at 25 °C for 5 min under 365 nm irradiation was applied for 3,13‐divinyl‐DDSQ (E1) with oxybis(2,1‐ethanediyloxy‐2,1‐ethanediyl) bis(3‐sulfanylpropanoate) (T1) as a bithiol monomer for linear and 2,2‐bis{[(3‐sulfanylpropanoyl)oxy]methyl}butyl 3‐sulfanylpropanoate (T2) as a trithiol monomer for soluble cross‐linked poly(thioether)s. All the resulting poly(thioether)s yielded colorless and transparent films by casting tetrahydrofuran solutions onto glass substrates. These polymers showed a higher decomposition temperature of 5 wt% loss over 350 °C. The films exhibited glass transition temperatures below 25 °C. Scratch scars were made on the surface of the cast films, and the self‐healing behavior was observed after heating at 40 °C. These results suggest that the DDSQ unit suppresses the molecular motion of the polymers and contributes to their self‐healing behavior.

A single-component LED excited enone photoinitiator for colorless and transparent antibacterial film preparation

Photoinitiators (PIs), as the key substances for photopolymerized antibacterial film (PAF), affect the cure rate and color of PAF. Herein, two enone dyes were designed and synthesized by a facile approach. Among the candidates, BDO1 has demonstrated the ability to initiate polymerization of acrylate monomers as single-component PI with the advantages of low mobility, outstanding photobleaching, excellent cytocompatibility, and suitability for light emitting diode (LED) light sources above 365 nm. Taking BDOs as examples, a novel method based on theoretical calculations aiming to assess the potential of enone molecules as single-component PIs was proposed. Finally, under the initiation of BDO1, tannic acid was photopolymerized to a colorless and transparent antibacterial film with high antibacterial ability, which indicated that BDO1 was expected to be used in environmentally friendly PAF.

Immobilization of rare-earth doped aluminate nanoparticles encapsulated with silica into polylactic acid-based color-tunable smart plastic window

An inorganic/organic nanocomposite was used to develop an afterglow and color-tunable smart window. A combination of polylactic acid (PLA) plastic waste as an environmentally-friendly hosting agent, and lanthanide-activated strontium aluminum oxide nanoparticles (SAON) encapsulated with silica nanoparticles (SAON@Silica) as a photoluminescent efficient agent resulted in a smart organic/inorganic nanocomposite. In order to prepare SAON-encapsulated silica nanoparticles (SAON@Silica), the SAON nanoparticles were coated with silica using the heterogeneous precipitation method. By using transmission electron microscopy (TEM), SAON showed a diameter range of 5–12 nm, while the SAON@Silica nanoparticles showed a diameter range of 50–100 nm. In order to ensure the development of a colorless plastic film, a homogeneous dispersion of the phosphorescent Phosphor@Silica nanoparticles throughout the plastic bulk was confirmed. CIE Lab coordinates and luminescence spectra were used to study the color shift characteristics. Under visible light conditions, the plastic films were transparent. The photoluminescent films emitted green light at 525 nm when excited at 375 nm. The hydrophobicity and ultraviolet protection were enhanced without altering the fundamental physico-mechanical performance of the plastic sheet. The current color-tunable plastic can be used in many potential applications, such as warning signs, anti-counterfeiting barcodes, smart windows, and protective apparel.

Monomer Dependence of Colorless and Transparent Polyimide Films: Thermomechanical Properties, Optical Transparency, and Solubility.

Six poly(amic acid)s (PAAs) were synthesized by reacting bis(3-aminophenyl) sulfone with various dianhydride monomers such as pyromellitic dianhydride, 4,4'-biphthalic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-oxidiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride. These PAAs were then converted to polyimide (PI) films by thermal imidization at various temperatures. To obtain colorless and transparent PI (CPI), the dianhydride monomer used in this study had an overall bent structure, a structure containing a strong electron-withdrawing -CF3 substituent or an alicyclic ring. In addition, some monomers contained ether or ketone functional groups in their bent structures. The thermomechanical properties, optical transparency, and solubility of CPI films with six different dianhydride monomer structures were investigated, and the correlation between the monomer structure and CPI film properties was clarified. Overall, CPI with an aromatic main chain structure or a linear structure had excellent thermal and mechanical properties. In contrast, CPI with a bent structure containing functional groups or substituents in the main chain exhibited excellent optical transparency and solubility.

Preparation and Properties of Mechanically Robust, Colorless, and Transparent Aramid Films.

In this study, various diamine monomers were used to synthesize aramid polymer films via a low-temperature solution condensation reaction with diacid chloride. For diamines with relatively high basicity, the reaction system became opaque because amine salt formation inhibited polymer synthesis. Meanwhile, low-basicity diamines with strong electron-withdrawing groups, such as CF3 and sulfone, were smoothly polymerized without amine salt formation to provide highly viscous solutions. The acid byproduct HCl generated during polymerization was removed by adding propylene oxide to the reaction vessel and converting the acid into highly volatile inert substances. The resulting solutions were used as varnishes without any additional purification, and polymer films with an excellent appearance were easily obtained through a conventional casting and convection drying process. The films neither tore nor broke when pulled or bent by hand; furthermore, even when heated up to 400 °C, they did not decompose or melt. Moreover, polymers prepared from 2,2-bis(trifluoromethyl)benzidine (TFMB) and bis(4-aminophenyl)sulfone (pAPS) did not exhibit glass transition until decomposition. The prepared polymer films showed a high elastic modulus of more than 4.1 GPa and a high tensile strength of more than 52 MPa. In particular, TFMB-, pAPS-, and 2,2-bis(4-aminophenyl)hexafluoropropane-based polymer films were colorless and transparent, with very high light transmittances of 95%, 96%, and 91%, respectively, at 420 nm and low yellow indexes of 2.4, 1.9, and 4.3, respectively.

Intrinsically Colored Polyimide Films Prepared by Embedding Chromophores on the Polymer Backbones

AbstractA versatile strategy of preparing colored polyimide (PI) films is developed by embedding colored monomers on the backbones of colorless substrate polymers. Intrinsically colored PI films of four colors—red, yellow, blue, and purple—are prepared by introducing relative chromophores to the substrate PI that are synthesized from 2,2′‐bis(trifluoromethyl)benzidine (TFMB) and 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA)—two widely used monomers for colorless and transparent PI films. In addition, a series of orange and green PI films are prepared by simple mixing of the red, yellow, or blue PIs. The properties of these colored PI films are characterized, exhibiting good mechanical, thermal, and solubility properties, as well as different color and brightness depending on the amounts and types of chromophores. The optical properties of these films are determined by UV–vis spectroscopy and Commission Internationale de I'Eclairage (CIE) Lab. It is demonstrated that the introduction of even small amounts of chromophores can afford spectrally colored films while maintaining the original benign properties of the substrate PIs.