Vibration-assisted vat photopolymerization for pixelated-aliasing-free surface fabrication

Mask image projection-based vat photopolymerization(MIP-VPP)offers advantages like low cost,high resolution,and a wide material range,making it popular in industry and education.Recently,MIP-VPP employing liquid crystal displays(LCDs)has gained traction,increasingly replacing digital micromirror devices,particularly among hobbyists and in educational settings,and is now beginning to be used in industrial environments.However,LCD-based MIP-VPPsuffers from pronounced pixelated aliasing arising from LCD’s discrete image pixels and itsdirect-contact configuration in MIP-VPP machines,leading to rough surfaces on the 3D-printed parts.Here,we propose a vibration-assisted MIP-VPP method that utilizes a microscalevibration to uniformize the light intensity distribution of the LCD-based mask image on VPP’s building platform.By maintaining the same fabrication speed,our technique generates asmoother,non-pixelated mask image,reducing the roughness on flat surfaces and boundary segments of 3D-printed parts.Through light intensity modeling and simulation,we derived an optimal vibration pattern for LCD mask images,subsequently validated by experiments.We assessed the surface texture,boundary integrity,and dimensional accuracy of componentsproduced using the vibration-assisted approach.The notably smoother surfaces and improved boundary roughness enhance the printing quality of MIP-VPP,enabling its promisingapplications in sectors like the production of 3D-printed optical devices and others.

Mechanistically Novel Frontal-Inspired In Situ Photopolymerization:An Efficient Electrode|Electrolyte Interface Engineering Method for High Energy Lithium Metal Polymer Batteries

The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.

Photopolymerization induced by a benzophenone derivative photoinitiator

A benzophenone derivative photoinitiator, HBP-TDI-HQ-TDI-HBP （HTCTH）, was synthesized based on 4-hydroxy benzophenone （HBP）, toluene-2,4-diisocyanate （TDI） and hydroquinone （HQ）. HTCTH was a more effective photoinitiator which had longer wavelength absorption in the UV-vis absorption spectra than the low molecular counterpart benzophenone （BP）. It showed that both rate of polymerization （Rp） and final conversion （P） increased with increase of amine and HTCTH concentration in photopolymerization.

DYE-SENSITIZED PHOTOPOLYMERIZATION OF METHYL METHACRYLATE INITIATED BY COUMARIN DYE/IODONIUM SALT SYSTEM

The photosensitive initiating system composed of 7-diethylamino-3-(2'-benzimidazolyl)coumarin dye (DEDC) and diphenyliodonium hexafluorophosphate (DIHP) which act as the sensitizer and the initiator respectively, can be used to initiate the polymerization of methyl methacrylate (MMA). The results showed that when exposed to visible light, coumarin dye/iodonium salt undergoes quick electron transfer from DEDC to DIHP and free radicals are produced. The visible light photoinduced reaction between DEDC and DIHP is mainly through the excited singlet state of DEDC and thus it is a little sensitive to O-2. The influence of concentration of DEDC, DIHP and MMA on the rate of photopolymerization of MMA was also investigated.

Novel preparation of monolithic imprinted columns for electrochromatographic separation by photopolymerization

A monolithic molecularly imprinted polymer with specific recognition ability for 4-hydroxybenzoic acid (4-HBA) was prepared by in situ photopolymerization, using methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, toluene and isooctane as porogenic solvents and Irgacure 1800 as an initiator. Baseline separation of isomers of hydroxybenzoic acid was achieved in less than 8 min on this monolithic column using 4-HBA as template, but not on the blank polymer. Furthermore, some neutral compounds could also be baseline-separated on the imprinted polymer column in the mode of pressure-driven capillary electrochromatography.

PHOTOPOLYMERIZATION OF PROPARGYL ACETATE WITH MICHLER’S KETONE AS PHOTOINITIATOR

Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator is described.

VISIBLE LIGHT PHOTOPOLYMERIZATION OF METHYL METHACRYLATE COINITIATED WITH TITANOCENE AND KETOCOUMARIN DYE

The photosensitive system which can initiate methyl methacrylate with visible light was composed of compound 1 bis( eta-5-cyclopentadienyl)-bis[2,6-difluoro-3-(1-H-pyrrolyl)phenyl]titanium (titanocene) and compound 2 [(3,3'-carbonylbis(7-diethylamino coumarin)] (ketocoumarin dye). The high photosensitive initiating efficiency of this photosensitive system could be very promising for efficient system for laser (Ar+ 488 nm) to plate and photocuring for thick coating and ink. The variation of UV-visible spectrum of compound 2 during irradiation indicates that photolysis of compound 2 is through its triplet state and it can be quenched by O-2 The much quicker photobleaching of the photosensitive system suggests that there exists certain quick electron transfer reaction between compounds 1 and 2.

Controlled Radical Photopolymerization of n-Butyl Methacrylate in Bluk Mediated by HTEMPO

Controlled radical photopolymerization of n-butyl methacrylate（n-BMA） mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy（HTEMPO） was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln（[Mo]/[M]） vs. time were liner respectively, indicating that was a controlled photopolymerization.

A natural component as initiator for photopolymerization of 1,6-hexanedioldiacrylate

1,3-Benzodioxole (BDO) as a simple model compound for the BDO derivatives from natural plant was used as coinitiator for p-chlorobenzophenone (CBP) and initiator for UV photopolymerization of 1,6-hexanedioldiacrylate (HDDA), respectively. The results showed that, BDO was an effective coinitiator for CBP. Although BDO as initiator led to very low rate of polymerization, it was still meaningful for the photocuring field.

PHOTOPOLYMERIZATION OF MMA INITIATED BY CYANINE DYE AND HEXAARYLBIIMIDAZ0LE

The photoinitiating system composed of 1-ethyl-3'-methylthiacyanine bro-mide (C-I), 2-chlorohexaarylbiimidazole (o-Cl-HABI) and 3-mercapto-4-methyl-4H-1, 2, 4-triazole (MTA), which act as sensitizer, initiator and hydrogen-donor respectively, can beused to initiate the polymerization of methyl methacrylate (MMA). The kinetic study wascarried out in trichloromathane solution at 30℃ by using dilatometry. The relation be-tween the polymerization rate and the concentrations of C-I, o-Cl-HABI, MTA and MMAwas studied.

DYE-SENSITIZED PHOTOLYSIS OF o-Cl-HEXAARYLBIIMIDAZOLE AND PHOTOPOLYMERIZATION KINETICS STUDY OF THE LONG WAVE-LENGTH DYE/HEXAARYLBIIMIDAZOLE SYSTEMS

o-Chloro-hexaarylbiimidazole (o-Cl-HABI) can be sensitized efficiently by the dyes 1-ethyl-3'-methyl thiacyanine bromide (C1), 3,3'-diethyl thiacarbocyanine iodide (C2), and cyclopentanone 2,5-bis[2-(1,3 -dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)ethylidene] (C3) through electron transfer proceses. When exposed to a xenon lamp (filtered by Pyrex glass), the photosensitive systems composed of o-Cl-HABI and the above dyes can produce free radicals which initiate the polymerization of MMA. The photopolymerization kinetics equation was obtained for the o-Cl-HABI/C2 system, R-p = K [C2](0.75)[o-Cl-HABI](0.44)[MTA](0.12)[MMA](1.0). A comparison of the influence of different dyes on the conversion of MMA photopolymerization was conducted.

THE PHOTOPOLYMERIZATION KINETICS OF PHOTOSENSITIZED ACRYLAMIDE SYSTEM INDUCED BY He-Ne LASER

The kinetics of the photopolymerization of sensitized acrylamide (AM) system induced by He-Ne laser has been investigated. Using methylene blue (MB)-triethanolamine (TEOA) as the photosensitive system, the photopolymerization followed a nonsteady-state kinetic scheme in the initial period of polymerization (the monomer conversion C%<2%) and then followed a steady-state kinetic scheme (5% >C%>2%). Accirding to the steady-state hypothesis, the mechanism of photopolymerization was proposed. The deduced kinetic equation of the photopolymerization of AM is in good coincidence with the experimental results.

The Photopolymerization Kinetics of Acryl amide Sensitized with Toluidine Blue-Alcoholamine Induced by He-Ne Laser

Toluidine blue(TB) is a good sensitizer for the polymerization of acrylnmide(AM) induced by He-Ne laser. With TB as a sensitizer and various alcoholamine as donors, the photoredox of TB and the polymerization kinetics of AM induced by He-Ne laser were investigated. It was found that either for the photoredox of TB or for the polymerization of AM, the activity of alcoholamine increases in the order of EOA<DEOA <TEOA in TB-alcoholamine sensitized system. The overall apparent kinetic equations of AM polymerization at 30℃ have been determined. In addition, the molecular weights under various conditions was measured.

Photopolymerization of Cyclohexene Oxide Initiated with Iron-arene Complex

Two iron-arene complex photoinitiators with different substituents in arene ligands were synthesized, their activities in initiating photopolymerization of cyclohexene oxide (CHO) were compared with that of IRGACURE 261, a commercialized photoinitiator from Ciba-Geigy. A higher activity was found when the arene ligand was substituted with a stronger electron donating group. For the system initiated by IRGACURE 261 the concentration of active centers in CHO polymerization was determined and it was found that the concentration is maximum at around 35℃. The post (dark) polymerization was significant, the polymerization yield decreased with the increase of irradiation temperature and increased with the increase of post polymerization temperature. The results are interpreted based on the mechanism proposed by Lohse, et al..

RADICAL PHOTOPOLYMERIZATION USING ARYLIODONIUM SALT/TERTIARY AMINE COMPLEX SYSTEM AS THE PHOTOINITIATOR

The diphenyliodonium salt (DPIOC)/triethylamine (TEA) is used as photoinitiator for radical photopolymerization. It was found that a ground state CT complex formed between DPIOC as electron acceptor and TEA as electron donor, which results in extending the photosensitivity range of DPIOC/TEA system up to above 500nm compared with DPIOC alone. The kinetic studies on photopolymerization of methyl methacrylate (MMA) were carried out in CH_3CN: H_2O (14: 1, v/v) mixture solution at 30℃ by dilatometer. The results obtained show that the polymerization rate (R_p) increases with increasing concentrations of DPIOC and TEA with exponent 0. 65 and 0. 62 respectively. The activation energy E_a and k_p/k_^(1/2) value were determined to be 4.1 Kcal mol^(-1) and 0.045 respectively. The other influence factors and reaction mechanism were also discussed.

Photopolymerization of Glycerin Triglycidyl Ether Based Systems

Photopolymerization process of glycerin triglycidyl ether based systems was studied by an FT-IR spectrometer.An increase in the rate of polymerization for glycerin triglycidyl ether was evident when 3,4-epoxycyclohexylmethyl-3＇,4＇-epoxycyclohexanecarboxylate was added to it.Its copolymerization mechanism was confirmed by using DSC analysis.The effect of ethoxylated trimethyol propane triacrylate on the rate of polymerization for glycerin triglycidyl ether was also studied,and the formation of interpenetrating network tightly cross-link was proposed.

PHOTOPOLYMERIZATION INITIATED BY DIMETHYLAMINOCHALCONE/DIPHENYLIODONIUM SALT COMBINATION SYSTEM SENSITIVE TO VISIBLE LIGHT

Several dimethylamino-substituted chalcone (i .e. dimethylaminobenzal acetophenone) (DBA) derivatives with intramolecular charge transfer transition character were used as visible light sensitizers for radical photopolymerization initiated by iodonium salt (DPIO). Initiating radical species is produced from DBA sensitized photolysis of DPIO through the single electron transfer, accompanying the bleaching of DBA, The activity of DBA decreases as a function of substituent attached to phenyl ring in the order: DBA-2 (OCH_3) >DBA-1(H)> DBA-3 (Cl). The kinetic study on photopolymerization of MMA was carried out in CH_3CN solution at 30 ℃ by dilatometry. The polymerization rate was determined to be proportional to the concentration with exponents of 0.42, 0.25 and 0.86 for DPIO, DBA-1 and MMA, respectively.

PREPARATION OF LOW MOLECULAR WEIGHT POLY(GLYCIDYL METHACRYLATE) BY PHOTOPOLYMERIZATION

Low molecular weight poly（glycidyl methacrylate）s （PGMAs） were prepared by photopolymerization in ethyl acetate, with benzophenone （BP） as photoinitiator, and triethylamine （TEA） as hydrogen donor. The existence of semipinacol dormant end groups in PGMA was confirmed by FT-IR and ^1H-NMR, and the content of the semipinacol dormant groups was determined quantitatively by ^1H-NMR measurement. The effects of various thctors, such as reaction time, BP concentration and monomer concentration on the synthesis of the polymers were investigated systematically. The molecular weights of the polymers were also investigated with GPC. It is shown that increasing BP concentration and decreasing irradiation time and monomer concentration led to a significant decrease of the molecular weights.

Photopolymerization of Dendritic Acrylated Aromatic/Aliphatic Polyesters and Properties of Their Cured Films

The radiative curable dendritic acrylated aromatic/aliphatic polyesters based on pentaerythritol, 1,2,4 benzenetricaboxylic anhydride and epoxy propane modified with acryloyl chloride were synthesized via a divergent procedure, and their photopolymerization kinetics was studied by photo differential scanning calorimetry. The mechanical properties and the morphology of the fracture surface of the cured dendritic polyester films were investigated by means of dynamic mechanical thermal analysis and scanning electron microscopy, respectively.