Vat photopolymerization(VPP)3D printing is an optimized technology for complex-shaped ceramic cores,in which the solid loading of ceramic slurries greatly infiuences the microstructure and property of the final cerami...Vat photopolymerization(VPP)3D printing is an optimized technology for complex-shaped ceramic cores,in which the solid loading of ceramic slurries greatly infiuences the microstructure and property of the final ceramic parts.However,the high solid loading of slurries is highly limited by the high viscosity.In this study,silica-based ceramic core slurries with solid loading up to 68vol.%were achieved by the composition design to optimize the performance,considering the curing,rheological,and double bond conversion rate.The slurries demonstrate superior curing and rheological performance with mass ratio of monomers being 3:2 and mass fraction of BYK111 being 4wt.%.Afterwards,the impact of solid loading on the morphology and mechanical properties was investigated.As the solid loading increases,the microstructure becomes gradually dense,leading to an improved flexural strength of 19.5 MPa.Additionally,the sintering shrinkage becomes more uniform,satisfying the casting requirements effectively.This work serves as a guide for the preparation of ceramic slurries with a high solid loading.展开更多
The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and...The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and structural-performance anisotropy limit the practical use of 3D-printed SiC components.Herein,a novel method is introduced to produce high-specific-strength SiC-based ceramics at a relatively low temperature of 1100℃.A mixed SiC/SiO_(2) slurry(30%SiO_(2) and 70%SiC by volume)with a solid loading of up to 40%was prepared to improve UV light penetration and printability.Additionally,incorporating a high content of methyl-phenyl-polysiloxane(PSO)solution(75%by weight)enabled low-temperature pyrolysis of SiC/SiO_(2)/PSO ceramics.The SiC/SiO_(2)/PSO ceramic lattices after pyrolysis achieved a specific strength as high as(1.03×10^(5))N·m·kg^(-1) and a density of 1.75 g·cm^(-3),outperforming similar SiC-based lattices structures of similar porosities.The bending strength of(95.49±8.79)MPa was comparable to that of ceramics sintered at 1400℃ or higher.Notably,the addition of the silicon carbide oxide(SiOC)phase reduced anisotropy,lowering the transverse and longitudinal compression strength ratios from 1.87 to 1.08,and improving mechanical properties by 79%.This improvement is attributed to SiOC shrinkage,promoting a uniform distribution of sintered components,resulting in a more robust and balanced material structure.This method offers valuable insight into the additive manufacturing(AM)of SiC-based ceramics at lower temperatures and provides new guidance for controlling anisotropy in 3D-printed ceramic parts.展开更多
Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF)...Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.展开更多
Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP)...Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP),and hybrid polymerization(HP)has been a charming research direction.Herein,we synthesized a novel cationic macro-PI(P-CSS)by copolymerizing polymerizable coumarin sulfonium salt(CSS)and methyl methacrylate(MMA).Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain.Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365,405 nm and under Laser@980 nm(with upconversion particles,UCPs).The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate(TMTPA)polymer is 1.25%of CSS,and in 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate(EPOX)polymer is 1.96%.These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.展开更多
The complex ceramic core used for hollow turbine blades requires a high porosity and a high fiexural strength. For a better balance between porosity and fiexural strength, ceramic materials with porous structures are ...The complex ceramic core used for hollow turbine blades requires a high porosity and a high fiexural strength. For a better balance between porosity and fiexural strength, ceramic materials with porous structures are preferred. In order to achieve the transition from disordered pore formation to ordered pore formation, Al_(2)O_(3) ceramic cores with triply periodic minimal surface(TPMS) micro lattice structures with different structural configurations(gyroid, diamond, and neovius) and different volume fractions of lattice structures(30, 40, and 50, vol.%) were designed and prepared by vat photopolymerization 3D printing. The effects of structural configuration and volume fraction of the lattice structure on the following structural shrinkage, microstructure, and flexural strength were investigated. The shrinkage relationship of the three lattice configurations is: neovius>diamond>gyroid. Besides, it is found that with an increase in the volume fraction of the 3D printed Al_(2)O_(3) ceramic micro lattice structures, their fiexural strength correspondingly increases ranging from 54.95 MPa to 139.1 MPa. The maximum average fiexural strength of the 3D printed Al_(2)O_(3) ceramic micro lattice structures is obtained when the structural configuration is diamond and with a volume fraction of 50vol.%, which is 139.1 MPa. Even when the volume fraction of the lattice structure is 30vol.%, that is to say the porosity is 70%, the fiexural strength is as high as 50-70 MPa, which can still be maintained at a high level. In addition, when the volume fraction of the lattice structure is a certain value, the sample with diamond configuration has a higher strength. The internal pore morphology, pore size, and porosity of the cores are precisely controlled, achieving both a high porosity and a high strength. Therefore, this study maintains high porosity and high strength simultaneously, providing a new lattice structure design idea for 3D printed ceramic cores.展开更多
To meet the evolving demands of aeroengine development,the structural and performance requirements for ceramic cores have become increasingly stringent.Vat photopolymerization 3D printing,owing to its moldless,fiexibl...To meet the evolving demands of aeroengine development,the structural and performance requirements for ceramic cores have become increasingly stringent.Vat photopolymerization 3D printing,owing to its moldless,fiexible manufacturing,and other advantages,demonstrates significant potential in the preparation of ceramic cores with intricate structures.However,its practical application still faces multiple challenges,including layered structures and property anisotropy,defects such as cracks and collapse during printing and sintering,forming inaccuracies,and difficulties in controlling surface roughness.Recent advances have focused on optimizing slurry formulation and rheology,improving curing behavior,introducing auxiliary powders and additives,tailoring forming parameters,and optimizing the sintering process.Nevertheless,effectively suppressing lamellar defects,achieving superior dimensional accuracy,and maintaining high surface quality in complex structures remain the core scientific and technical issues to be solved.Future research should concentrate on refining curing mechanisms,advancing powder design and organic system optimization,and regulating the coupled processes of forming,debinding,and sintering to accelerate the application of VPP 3D printed ceramic cores in aerospace manufacturing.展开更多
HTEMPO-functionalized central cores were formed with divinylbenzene in ＇＇core first＇＇ method,and the four or five arms star polymers were built via controlled/living free radical photopolymerization.The four arms ...HTEMPO-functionalized central cores were formed with divinylbenzene in ＇＇core first＇＇ method,and the four or five arms star polymers were built via controlled/living free radical photopolymerization.The four arms star polymers were also prepared with controlled/living free radical photopolymerization in ＇＇arm first＇＇ method.The resulting polymers had been confirmed by GPC and 1 H NMR.It showed that the star polymers had low polydispersities and molecular weight（M n） with the 85,000-560,000 g/mol range.展开更多
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 pho...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.展开更多
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 ha...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.展开更多
Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized ...Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.展开更多
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, ...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.展开更多
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, ethylen...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.展开更多
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...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.展开更多
Thioxanthone-based N-phthalimidoamino acid ammonium salt（thioxanthen-DBU） as a photocaged base was synthesized and characterized. The photochemical properties and initiation mechanism were analyzed. It was found tha...Thioxanthone-based N-phthalimidoamino acid ammonium salt（thioxanthen-DBU） as a photocaged base was synthesized and characterized. The photochemical properties and initiation mechanism were analyzed. It was found that the compound absorbs over the UV and visible region with relatively high absorption coefficients. Furthermore, the covalent binding of N-phthalimidoamino acid and type II chromophores（thioxanthone, TX） remarkably improved the photoreactivity. Specifically, in combination with a benzoyl peroxide initiator, thioxanthen-DBU was able to initiate the amine-mediated redox photopolymerization of trimethylol propane triacrylate（TMPTA）, and an excellent photopolymerization profile was obtained.展开更多
Vat photopolymerization(VPP)3D printing technology has broken through mold limitations and shown great potential to manufacture complex-structured ceramic cores for turbine blades.However,improving dimensional accurac...Vat photopolymerization(VPP)3D printing technology has broken through mold limitations and shown great potential to manufacture complex-structured ceramic cores for turbine blades.However,improving dimensional accuracy is difficult for the VPP 3D printed parts due to the high contraction deformation.Reducing shrinkage is a key challenge for developing 3D-printed ceramic cores.In this study,3D-printed alumina ceramic cores with near-zero shrinkage in the X direction were achieved for the first time using a novel approach that was called atmosphere-controlled in-situ oxidation of aluminum powder.The in-situ oxidation reaction of the aluminum powder was creatively tuned by changing the atmosphere transition temperature from argon to air.Then,the microstructure and properties of the ceramic core could be controlled by the liquid-phase sintering with the participation of atmosphere-protected molten aluminum.As a result,the pore size of the ceramic cores was significantly increased by almost ten times,but the bonding strength of the grains was also increased.In addition,the powder consolidation generated by the action of molten aluminum was considered to be an important reason for reducing the linear shrinkage of ceramic cores.Under the optimized parameters,the linear shrinkage of the ceramic cores was as low as 0.3%in the X direction.The high apparent porosity(45.02%)and flexural strength(72.7 MPa)of the alumina ceramic cores were realized at the same time.The in-situ control of sintering by changing the atmosphere will be a creative method for regulating the properties of ceramic materials.展开更多
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 ...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.展开更多
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 -dihy...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.展开更多
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 ...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.展开更多
Bioprinting is emerging as an advanced tool in tissue engineering.However,there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors.In this study,modifie...Bioprinting is emerging as an advanced tool in tissue engineering.However,there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors.In this study,modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing(DLP)printing.The Plasma-MA(BM)was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride.The methacry-lated levels were observed to influence the physical properties of BM hydrogels including mechanical properties,swelling,and degradation.The photo-crosslinked BM hydrogels can sustainedly release vascu-lar endothelial growth factor(VEGF)and exhibit positive biological effects on cell adhesion and prolifer-ation,and cell functionality such as tube formation of human umbilical vein endothelial cells(HUVECs),and neurite elongation of rat pheochromocytoma cells(PC12).Meanwhile,BM hydrogels can also induce cell infiltration,modulate immune response,and promote angiogenesis in vivo.Moreover,the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process.These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.展开更多
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-epoxycyclohexy...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.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52102062)the Xi’an Science and Technology Plan Project(No.23LLRH0004)the Key Research and Development Project of Shaanxi Province of China(2024GX-YBXM-352)。
文摘Vat photopolymerization(VPP)3D printing is an optimized technology for complex-shaped ceramic cores,in which the solid loading of ceramic slurries greatly infiuences the microstructure and property of the final ceramic parts.However,the high solid loading of slurries is highly limited by the high viscosity.In this study,silica-based ceramic core slurries with solid loading up to 68vol.%were achieved by the composition design to optimize the performance,considering the curing,rheological,and double bond conversion rate.The slurries demonstrate superior curing and rheological performance with mass ratio of monomers being 3:2 and mass fraction of BYK111 being 4wt.%.Afterwards,the impact of solid loading on the morphology and mechanical properties was investigated.As the solid loading increases,the microstructure becomes gradually dense,leading to an improved flexural strength of 19.5 MPa.Additionally,the sintering shrinkage becomes more uniform,satisfying the casting requirements effectively.This work serves as a guide for the preparation of ceramic slurries with a high solid loading.
基金financially supported by the Key Project of Department of Education of Guangdong Province(Grant No.2022ZDZX3017)Special Support Plan of Guangdong Province(Grant No.2021TQ05Z151)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515010049)SZU Research Fund(Grant No.GFPY-YB-2024-03)Shenzhen Science and Technology Programs(Grant Nos.GJHZ20210705141803011 and 20200731211324001).
文摘The combination of silicon carbide(SiC)ceramics and stereolithography technology shows promise for manufacturing complex-shaped SiC components,expanding application possibilities.However,high sintering temperature and structural-performance anisotropy limit the practical use of 3D-printed SiC components.Herein,a novel method is introduced to produce high-specific-strength SiC-based ceramics at a relatively low temperature of 1100℃.A mixed SiC/SiO_(2) slurry(30%SiO_(2) and 70%SiC by volume)with a solid loading of up to 40%was prepared to improve UV light penetration and printability.Additionally,incorporating a high content of methyl-phenyl-polysiloxane(PSO)solution(75%by weight)enabled low-temperature pyrolysis of SiC/SiO_(2)/PSO ceramics.The SiC/SiO_(2)/PSO ceramic lattices after pyrolysis achieved a specific strength as high as(1.03×10^(5))N·m·kg^(-1) and a density of 1.75 g·cm^(-3),outperforming similar SiC-based lattices structures of similar porosities.The bending strength of(95.49±8.79)MPa was comparable to that of ceramics sintered at 1400℃ or higher.Notably,the addition of the silicon carbide oxide(SiOC)phase reduced anisotropy,lowering the transverse and longitudinal compression strength ratios from 1.87 to 1.08,and improving mechanical properties by 79%.This improvement is attributed to SiOC shrinkage,promoting a uniform distribution of sintered components,resulting in a more robust and balanced material structure.This method offers valuable insight into the additive manufacturing(AM)of SiC-based ceramics at lower temperatures and provides new guidance for controlling anisotropy in 3D-printed ceramic parts.
基金the financial support of the Tianjin Technical Expert Project(22YDTPJC00620)。
文摘Pyrrolo[3,2-b]pyrrole is a good building block for radical photoini-tiators.In this study,free-radical photoinitiator 1,4-bis(4-bro-mophenyl)-2,5-bis(4-(trifluo-romethyl)phenyl)-1,4-dihydropy-rrolo[3,2-b]pyrrole(PyBF),con-taining a symmetric trifluo-romethyl(-CF3)end group,is syn-thesized via a one-step aldehyde-ketone condensation re-action for light-emitting diode(LED)photopolymerization.The-CF3 groups are incorporated into the 2,5-phenyl on the pyrrolo[3,2-b]pyrrole core.PyBF rapidly initiates the photopolymerization of acrylate pre-polymers and monomers under LED illumination at 365 and 405 nm.A possible photolysis mechanism is provided.In the presence of amines,PyBF increases the gel fraction rate of polyethylene glycol diacrylate(PEGDA)from 63.4%to 80.0%,indicating good potential as a two-component photoinitiator.PyBF exhibits a thermal decomposition temperature in an ex-cess of 300℃,comparable to that of a commercial photoinitiator(diphenyl(2,4,6-trimethyl-benzoyl)phosphine oxide,TPO),indicating its thermal stability.PyBF shows low migration in light-curing materials.Scanning electron microscopy images indicate that the materials of the PyBF/TPO/PEGDA mixture cured using the PyBF/TPO two-component photoinitia-tor system exhibit a smooth surface,in contrast to those cured with PyBF/PEGDA and TPO/PEGDA systems.The cured materials also display low curing shrinkage.Therefore,the pyrrolo[3,2-b]pyrrole radical photoinitiator exhibits high photoactivity in visible-light pho-topolymerization reactions.
基金financial support by the National Natural Science Foundation of China(Nos.22301107,52373057)Nature Science Foundation of Jiangsu Province(No.BK20242080)+1 种基金Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,Jiangnan University(No.1042050205243170/008)State Key Laboratory of Molecular Engineering of Polymers,Fudan University(No.K2024-39).
文摘Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP),and hybrid polymerization(HP)has been a charming research direction.Herein,we synthesized a novel cationic macro-PI(P-CSS)by copolymerizing polymerizable coumarin sulfonium salt(CSS)and methyl methacrylate(MMA).Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain.Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365,405 nm and under Laser@980 nm(with upconversion particles,UCPs).The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate(TMTPA)polymer is 1.25%of CSS,and in 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate(EPOX)polymer is 1.96%.These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.
基金supported by the National Natural Science Foundation of China (Grant No. 52275310)。
文摘The complex ceramic core used for hollow turbine blades requires a high porosity and a high fiexural strength. For a better balance between porosity and fiexural strength, ceramic materials with porous structures are preferred. In order to achieve the transition from disordered pore formation to ordered pore formation, Al_(2)O_(3) ceramic cores with triply periodic minimal surface(TPMS) micro lattice structures with different structural configurations(gyroid, diamond, and neovius) and different volume fractions of lattice structures(30, 40, and 50, vol.%) were designed and prepared by vat photopolymerization 3D printing. The effects of structural configuration and volume fraction of the lattice structure on the following structural shrinkage, microstructure, and flexural strength were investigated. The shrinkage relationship of the three lattice configurations is: neovius>diamond>gyroid. Besides, it is found that with an increase in the volume fraction of the 3D printed Al_(2)O_(3) ceramic micro lattice structures, their fiexural strength correspondingly increases ranging from 54.95 MPa to 139.1 MPa. The maximum average fiexural strength of the 3D printed Al_(2)O_(3) ceramic micro lattice structures is obtained when the structural configuration is diamond and with a volume fraction of 50vol.%, which is 139.1 MPa. Even when the volume fraction of the lattice structure is 30vol.%, that is to say the porosity is 70%, the fiexural strength is as high as 50-70 MPa, which can still be maintained at a high level. In addition, when the volume fraction of the lattice structure is a certain value, the sample with diamond configuration has a higher strength. The internal pore morphology, pore size, and porosity of the cores are precisely controlled, achieving both a high porosity and a high strength. Therefore, this study maintains high porosity and high strength simultaneously, providing a new lattice structure design idea for 3D printed ceramic cores.
基金supported by the National Key R&D Program of China(Grant Nos.2024YFB3714502,2024YFB3714501,2024YFB3714504)the National Natural Science Foundation of China(Grant Nos.52130204,52174376)+5 种基金the TQ Innovation Foundation(Grant No.23-TQ09-02-ZT-01-005)the Aeronautical Science Foundation of China(Grant No.20220042053001)the Ningbo Science and Technology Plan Project(Grant No.2025Z070)the Key R&D Project of Shaanxi Province(Grant Nos2024GX-YBXM-220,2024CY-GJHX-29,2024GX-ZDCYL-03-03,2024GX-YBXM-400)the National Advanced Rare Metal Materials Innovation Center Project[Grant No.2024 ZG-GCZX-01(1)-01]the Foundation of China Scholarship Council(Grant No.202406290136)。
文摘To meet the evolving demands of aeroengine development,the structural and performance requirements for ceramic cores have become increasingly stringent.Vat photopolymerization 3D printing,owing to its moldless,fiexible manufacturing,and other advantages,demonstrates significant potential in the preparation of ceramic cores with intricate structures.However,its practical application still faces multiple challenges,including layered structures and property anisotropy,defects such as cracks and collapse during printing and sintering,forming inaccuracies,and difficulties in controlling surface roughness.Recent advances have focused on optimizing slurry formulation and rheology,improving curing behavior,introducing auxiliary powders and additives,tailoring forming parameters,and optimizing the sintering process.Nevertheless,effectively suppressing lamellar defects,achieving superior dimensional accuracy,and maintaining high surface quality in complex structures remain the core scientific and technical issues to be solved.Future research should concentrate on refining curing mechanisms,advancing powder design and organic system optimization,and regulating the coupled processes of forming,debinding,and sintering to accelerate the application of VPP 3D printed ceramic cores in aerospace manufacturing.
文摘HTEMPO-functionalized central cores were formed with divinylbenzene in ＇＇core first＇＇ method,and the four or five arms star polymers were built via controlled/living free radical photopolymerization.The four arms star polymers were also prepared with controlled/living free radical photopolymerization in ＇＇arm first＇＇ method.The resulting polymers had been confirmed by GPC and 1 H NMR.It showed that the star polymers had low polydispersities and molecular weight（M n） with the 85,000-560,000 g/mol range.
基金the National Natural Science Foundation of China(No.50473024)for its financial support.
文摘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.
基金The support provided by the German Federal Ministry of Education and Research(BMBF)within the project“Benchbatt”(03XP0047B)is gratefully acknowledged.
文摘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.
基金the financial support by the National Natural Science Foundation of China(Nos.22301107,52373057)the Nature Science Foundation of Jiangsu Province(No.BK20200610)+1 种基金the Fundamental Research Funds for the Central Universities(No.JUSRP122021)Jiangsu Province"Innovation and Entrepreneurship Doctor"Talent Plan(No.JSSCBS20221053)also provided support。
文摘Developing efficient and long wavelength sensitive unimolecular photoinitiators(PIs)is still facing a great challenge.In this work,a series of thioxanthone-based N-hydroxyphthalimide esters(TX-NHPIEs)were synthesized by installing NHPIEs along the TX backbone and characterized.The investigated TX-NHPIEs have a 60 nm redshift and demonstrate sterling initiating efficiency for free radical photopolymerization(FRP)under LED@450 nm light irradiation compared with the commercialized isopropylthioxanthone(ITX).Real-time1Hnuclear magnetic resonance(1H NMR),electron spin resonance(ESR),decarboxylation and gas chromatograph-mass spectrometer(GC–MS)experiments and density functional theory(DFT)reveal that TX-NHPIEs can generate one alkyl radical and one N-centered iminyl radical,which can initiate FRP directly and indirectly,respectively.In other words,TX-NHPIEs absorb one photon and can generate two active radicals,which break through the limitations of common PIs.TX-NHPIE-Cpe demonstrates the highest initiating efficiency,and its application in coatings and 3D printing was also studied,indicating TX-NHPIEs have broad potential applications in photopolymerization processes.
基金This work was supported by the National Natural Science Foundation of China (No. 59773011).
文摘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.
文摘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.
文摘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.
基金financially supported by National Natural Science Foundation of China(No.20974127,21374135)China Postdoctoral Science Foundation(No.2013M542178)+1 种基金the Open Foundation of the State Key Laboratory of Pulp and Paper Engineering in South China University of Technology(No.C713043z)the Fundamental Research Funds for the Central Universities(No.2013ZB0025)
文摘Thioxanthone-based N-phthalimidoamino acid ammonium salt（thioxanthen-DBU） as a photocaged base was synthesized and characterized. The photochemical properties and initiation mechanism were analyzed. It was found that the compound absorbs over the UV and visible region with relatively high absorption coefficients. Furthermore, the covalent binding of N-phthalimidoamino acid and type II chromophores（thioxanthone, TX） remarkably improved the photoreactivity. Specifically, in combination with a benzoyl peroxide initiator, thioxanthen-DBU was able to initiate the amine-mediated redox photopolymerization of trimethylol propane triacrylate（TMPTA）, and an excellent photopolymerization profile was obtained.
基金the National Natural Science Foundation of China(Nos.52130204,52174376)the Guangdong Basic and Ap-plied Basic Research Foundation(No.2021B1515120028)+6 种基金the Sci-ence and Technology Innovation Team Plan of Shaan Xi Province(No.2021TD-17)the Youth Innovation Team of Shaanxi Univer-sities,Xi’an Science and Technology Program(No.21ZCZZHXJS-QCY6-0005)the Fundamental Research Funds for the Central Uni-versities(Nos.D5000230348,D5000210902)the TQ Innovation Foundation(No.23-TQ09-02-ZT-01-005)the Aeronautical Science Foundation of China(No.20220042053001)the Thousands Person Plan of Jiangxi Province(No.grant number JXSQ2020102131)the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(No.CX2022033),China.
文摘Vat photopolymerization(VPP)3D printing technology has broken through mold limitations and shown great potential to manufacture complex-structured ceramic cores for turbine blades.However,improving dimensional accuracy is difficult for the VPP 3D printed parts due to the high contraction deformation.Reducing shrinkage is a key challenge for developing 3D-printed ceramic cores.In this study,3D-printed alumina ceramic cores with near-zero shrinkage in the X direction were achieved for the first time using a novel approach that was called atmosphere-controlled in-situ oxidation of aluminum powder.The in-situ oxidation reaction of the aluminum powder was creatively tuned by changing the atmosphere transition temperature from argon to air.Then,the microstructure and properties of the ceramic core could be controlled by the liquid-phase sintering with the participation of atmosphere-protected molten aluminum.As a result,the pore size of the ceramic cores was significantly increased by almost ten times,but the bonding strength of the grains was also increased.In addition,the powder consolidation generated by the action of molten aluminum was considered to be an important reason for reducing the linear shrinkage of ceramic cores.Under the optimized parameters,the linear shrinkage of the ceramic cores was as low as 0.3%in the X direction.The high apparent porosity(45.02%)and flexural strength(72.7 MPa)of the alumina ceramic cores were realized at the same time.The in-situ control of sintering by changing the atmosphere will be a creative method for regulating the properties of ceramic materials.
基金This work was financially supported by the National Nature Science Foundation of China (Project number: 59773011).
文摘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.
基金This project financially supported by National Natural Science Foundation of China (Project number 59973023)
文摘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.
文摘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.
基金supported by the National Natural Science Foundation(No.32271468)Sichuan Science and Technology Program(No.2021JDTD0001)+2 种基金Natural Science Foundation of Sichuan Province(No.2022NSFSC1280)Post-Doctor Research Project,West China Hospital,Sichuan University(No.2023HXBH081)Sichuan Science and Technology Program(No.2021YFS0124)。
文摘Bioprinting is emerging as an advanced tool in tissue engineering.However,there is still a lack of bioinks able to form hydrogels with desirable bioactivities that support positive cell behaviors.In this study,modified plasma proteins capable of forming hydrogels with multiple biological functions are developed as bioinks for digital light processing(DLP)printing.The Plasma-MA(BM)was synthesized via a one-pot method through the reaction between the fresh frozen plasma and methacrylic anhydride.The methacry-lated levels were observed to influence the physical properties of BM hydrogels including mechanical properties,swelling,and degradation.The photo-crosslinked BM hydrogels can sustainedly release vascu-lar endothelial growth factor(VEGF)and exhibit positive biological effects on cell adhesion and prolifer-ation,and cell functionality such as tube formation of human umbilical vein endothelial cells(HUVECs),and neurite elongation of rat pheochromocytoma cells(PC12).Meanwhile,BM hydrogels can also induce cell infiltration,modulate immune response,and promote angiogenesis in vivo.Moreover,the plasma bioinks can be used to fabricate customized scaffolds with complex structures through a DLP printing process.These findings implicate that the modified plasma with growth factor release is a promising candidate for bioprinting in autologous and personalized tissue engineering.
基金Funded by the Innovatory Group Program of the Natural Science Foundation of Hubei Province (2004ABC001)the National "863" Hi-tech Foundation of China (2002AA6Z3083)
文摘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.
