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Enhanced plasticity of spontaneous coagulation cast oxide ceramic green bodies

Journal of Advanced Ceramics 2024年第5期13卷 568-578页

作者： Juanjuan Wang Jin Zhao Junyan Mao Wenlong Liu Haohao Ji Jian Zhang Shiwei Wang State Key Laboratory of High Performance Ceramics and Superfine Microstructure Shanghai Institute of CeramicsChinese Academy of SciencesShanghai 200050China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China

In the preparation of large-sized ceramics,the use of a green body with relatively high plasticity is crucial to minimize the risk of cracking during processing.To achieve this goal,glycerol and polyethylene glycol(PEG)were utilized as plasticizers in the shaping of green bodies of oxide ceramics through spontaneous coagulation casting(SCC).This study investigated the effects of plasticizers and particle sizes ranging from the submicron to nanoscale on the slurry viscosity,drying shrinkage of wet gels,and mechanical properties of green bodies.The plasticity of the green bodies was assessed by measuring the impact toughness and flexural stress‒strain curves.By incorporating an appropriate plasticizer,the peak width of the flexural stress‒strain curve for dried green bodies from particles of different sizes was nearly twice that without plasticizers,and the impact toughness was enhanced by approximately 71%,34%,and 41%when the particle size decreased from the submicron scale to the nanoscale(0.45μm,0.18μm,and 50 nm,respectively).The drilling test revealed that there was nearly no cracking around the holes in the green bodies with plasticizers.The plasticity mechanism of the green bodies was examined based on ultraviolet–visible(UV–Vis)spectroscopy and scanning electron microscopy(SEM).It was discovered that plasticizers might mitigate the brittleness of green bodies by adjusting the interactions between molecules and modifying the gel network properly.

关键词： green body plasticity plasticizer particle size impact toughness stress-strain curve

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Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral)(PVB) as Elucidated by Solid-State NMR

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Chinese Journal of Polymer Science 2024年第1期42卷 113-124,I0010页

作者： Jing Lv Xu Chen Zi-Shuo Wu Ya-Hui Li Wei Chen National Synchrotron Radiation Laboratory Anhui Provincial Engineering Laboratory of Advanced Functional Polymer FilmCAS Key Laboratory of Soft Matter ChemistryUniversity of Scienceand Technology of ChinaHefei 230026China

The chain dynamics heterogeneity of the poly(vinyl butyral)(PVB) plasticized by triethylene glycol bis(2-ethylhexa noate)(TEG-EH) was investigated by various solid-state NMR techniques.The plasticized PVB shows two domains in distinct molecular dynamics differences,namely,rigid and soft domains,where the latter is the plasticizer-rich domain.The time domain low field NMR was first used to investigate the dynamics heterogeneity of the plasticized PVB,and the results show the decreasing activated energy of components in the soft domain of plasticized PVB(E_a=20.2 kJ/mol) as compared with that of the pristine one(E_a=24.3 kJ/mol).Detailed dynamics heterogeneity was obtained by high-field NMR with site-specific features.The quadrupole-echo ~2H-NMR was adopted to elucidate the dynamics heterogeneity of the vinyl alcohol(VA) units,where only the hydroxyl group of VA is deuterated.The ~1H-^(13)C WISE NMR spectra show that there is not much difference in the mobility of the VB unit in PVB with and without plasticizer,whereas the glass transition temperature differed by approximately 53℃.This is further supported by Torchia's T_1 relaxation measurements.The origin of such an unusual phenomenon is attributed to the critical role of the remaining VA(~22%) in the soft domain,where the VA units locally aggregate through hydrogen bonding.Also,the existence of a mobility gradient in the VB unit has been demonstrated.Moreover,the mobility difference for VB with different stereo-geometry(meso or racemic conformation) is observed for the first time.This indicates the importance of modulating the ratio of meso over racemic VB for controlling the macroscopic perfo rmance of PVB.

关键词： Poly(vinyl butyral) Dynamics heterogeneity plasticizer Solid state NMR

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Phosphorus Containing Rubber Seed oil as a Flame Retardant plasticizer for Polyvinyl Chloride

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Journal of Renewable Materials 2023年第4期11卷 1731-1743页

作者： Hongying Chu Huabei Li Xiaoyan Sun Yaowang Zhang Yellow River Conservancy Technical Institute Kaifeng475004China Henan Engineering Technology Research Center of Green Coating Materials Kaifeng475004China

The application of phthalate plasticizers has been restricted around the world due to their poor migration and potential harm to the human body.Hence,producing functional bio-based plasticizers via exploiting clean and reusable resources meets the satisfaction of current demands.In this study,flame-retardant rubber seed oil-based plasticize(FRP)was prepared via epoxidation reaction and ring opening addition reactions,which was used as a flame-resistant plasticizer for polyvinyl chloride to replace petroleum-based phthalate plasticizer.When DOP was replaced with FRP,the torque of PVC blends increased from 11.4 to 18.4 N⋅m,the LOI value increased from 24.3%for PVC-FRP-0%to 33.1%for PVC-FRP-20.The THR value diminished from 39 MJ/m^(2)(pertaining to PVC-FRC-0)to 22 MJ/m^(2)Tg increased from 23°C to 47°C,the weight loss of plasticized PVC blends significantly reduced from 22.6%to 2.8%in leaching tests.The study provided a new way to prepare flame retardant plasticizer using rubber seed oil as raw material.

关键词： plasticizer rubber seed oil polyvinyl chloride vegetable oil modification

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Surface sulfur vacancies enhanced electron transfer over Co-ZnS quantum dots for efficient degradation of plasticizer micropollutants by peroxymonosulfate activation

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Chinese Chemical Letters 2022年第8期33卷 3829-3834页

作者： Yuting Gu Tingting Gao Fagen Zhang Chao Lu Wenrui Cao Ziwei Fu Chun Hu Lai Lyu Key Laboratory for Water Quality and Conservation of the Pearl River Delta Ministry of EducationInstitute of Environmental Research at Greater BayGuangzhou UniversityGuangzhou 510006China Shandong Key Laboratory of Water Pollution Control and Resource Reuse School of Environmental Science and EngineeringShandong UniversityQingdao 266237China School of Environmental Science and Engineering Guangzhou UniversityGuangzhou 510006China Institute of Rural Revitalization Guangzhou UniversityGuangzhou 510006China

Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cycling rate limitation.Herein,a new strategy is proposed based on a quantum dots(QDs)/PMS system.Co-ZnS QDs are synthesized by a water phase coprecipitation method.The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies(SVs),which modulates the surface of the catalyst to form an electronic nonequilibrium surface.Astonishingly,the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-Zn S QDs/PMS system due to this type of surface modulation.The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors,where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs.Meanwhile,PMS adsorbed on the SVs is reduced to radicals by capturing electrons,achieving effective electron recovery.Dissolved oxygen(DO)molecules are also easily attracted to catalyst defects and are reduced to O_(2)^(·-),further promoting the degradation of pollutants.

关键词： Peroxymonosulfate activation Sulfur vacancy Quantum dots ZnS plasticizer

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EFFECT OF plasticizer ON THE MICROSTRUCTURE OF PS/PVC BLENDS

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Chinese Journal of Polymer Science 1996年第3期14卷 193-198页

作者：乔金梁 D.Vesely Beijing Research Institute of Chemical Industry The Ministry of Chemical Industry Beijing 100013 Department of Material Technology Brunel University Uxbridge London UB8 3PH UK

In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.

关键词： viscosity ratio microstructure polystyrene PVC blending plasticizer

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Using an Inhibitor to Prevent plasticizer Migration from Polyurethane Matrix to EPDM Based Substrate

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Chinese Journal of Polymer Science 2019年第7期37卷 681-686页

作者： Hadi Rezaei-Vahidian Tohid Farajpour Mahdi Abdollahi Space Transportation Research Institute Iranian Space Research CenterTehranIran Polymer Reaction Engineering Department Faculty of Chemical EngineeringTarbiat Modares UniversityTehranIran

The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the polyurethane (PU) binder containing DOP plasticizer was used as a polymeric matrix and β-cyclodextrin (β-CD) was applied as inhibitor agent to prevent plasticizer migration from the PU matrix into the ethylene propylene diene monomer (EPDM) substrate. To increase the compatibility of β-CD and PU matrix, a derivative of β-CD has been synthesized using toluene diisocyanate (β-CD-TDI). The synthesized derivative was characterized by MALDI-MS and FTIR-ATR analyses. FTIR-ATR results confirmed the formation of bonding between β-CD and the polymeric network while the MALDIMS results showed that the synthesized derivative contained two β-CD and 7 TDI molecules bonded to β-CD. Investigation of the mechanical properties of PU modified by β-CD-TDI showed a decrease in tensile strength and an increase in elongation at break with increasing β-CD-TDI content. DMTA results showed a decrement in crosslinking density by increasing the β-CD-TDI content. Also, to investigate plasticizer migration, extraction of the DOP plasticizer from samples was performed using dichloromethane solvent and its concentration was measured by gas chromatography. The results of migration evaluation after four months showed that using β-CD as an inhibitor agent in the PU binder could prevent the migration of plasticizer to EPDM substrate.

关键词： plasticizer migration β-Cyclodextrin Polyurethane

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Studies on Epoxidised Castor Oil as Co-plasticizer with Epoxidised Soyabean Oil for PVC Processing

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Journal of Renewable Materials 2019年第8期7卷 775-785页

作者： Gouni Thirupathiah Sukanya Satapathy Aruna Palanisamy Polymers&Functional Materials Division Indian Institute of Chemical TechnologyUppal RoadTarnakaHyderabad500007Telangana StateIndia

An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.

关键词： PVC plasticizer epoxidised castor oil tensile strength

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Synthesis of aliphatic amidediol and used as a novel mixed plasticizer for thermoplastic starch

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Chinese Chemical Letters 2008年第4期19卷 395-398页

作者： Jian She Zhang Jiu Gao Yu Ying Wu Xiao Fei Ma School of Science Tianjin UniversityTianjin 300072PR China

In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.

关键词： Thermoplastic starch Aliphatic amidediol Glycerol plasticizer

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Effect of plasticizer Poly(Ethylene Glycol)on the Crystallization Properties of Stereocomplex-Type Poly(Lactide Acid)

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Wuhan University Journal of Natural Sciences 2017年第5期22卷 420-428页

作者： CUI Li ZHANG Rundong WANG Yahui ZHANG Chuanjie GUO Yi Hubei Key Laboratory of Biomass Fibers and Eco-dyeing&Finishing Wuhan Textile UniversityWuhan 430073HubeiChina

The effects of the plasticizer poly（ethylene glycol）（PEG） on crystallization properties of equimolar poly（L-lactide）（PLLA）/poly（D-lactide）（PDLA） blends were investigated. Forma- tion of the stereocomplex-type poly（lactide acid）（sc-PLA） crystallites was confirmed by Wide-angle X-ray diffraction （WAXD） and differential scanning calorimetry （DSC） analyses. Sc-PLA crystallites without any homochiral poly（lactide acid）（hc-PLA） formed, as the result of the incorporation of the plasticizer PEG （more than or equal to 10%（wt）） at a processing temperature （240 ℃）. More-over, when the Mw of PEG reached 1 000 g · mol^-1, the crystal- lizability of stereocomplex crystallites was the best. Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA, with the optimum crystallization kinetic parameters being obtained at 10% （wt） PEG. Several crys- tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA. The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves- tigated using polarized optical microscopy.

关键词： plasticizer stereocomplex-type poly（lactide acid） crystallization

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A simple approach with scale-up potential towards intrinsically flame-retardant biobased co-plasticizer for PVC artificial materials

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Journal of Leather Science and Engineering 2020年第1期2卷 86-94页

作者： Yong Xu Songhang Wang Jinming Chang Zhou Xu Qi Zeng Zhonghui Wang Jun Yan Yi Chen College of Biomass Science and Engineering Sichuan UniversityChengdu 610065P.R.China Key Laboratory of Leather Chemistry and Engineering of Ministry of Education Sichuan UniversityChengdu 610065P.R.China Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province China West Normal UniversityNanchong 637009P.R.China Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province College of Chemistry and Chemical EngineeringChina West Normal UniversityNanchong 637000P.R.China School of Life Science and Food Engineering Yibin UniversityYibin 644007P.R.China

As an imitation of genuine leather,polyvinyl chloride(PVC)artificial materials are versatile,but suffers from being flammable due to the presence of large amounts of combustible plasticizers.Under such circumstance,intrinsically flame-retardant plasticizers displaying dual functions have been a subject of intensive research interest.However,previous strategies attempting to covalently attach flame-retardant moiety to plasticizers invariably required either expensive starting materials or laborious and tedious procedures,ultimately limiting their scale-up application in industry.In addition,driven by escalating demand of halogen-free flame retardants worldwide from an environmental health perspective,previously reported intrinsically flame-retardant plasticizers were mainly halogenfree,less attractive in PVC artificial material industry simply because PVC itself is a halogen-containing polymer.Here,we report an approach to introduce chlorine moieties into unsaturated fatty acid methyl ester by a simple addition reaction occurring on carbon-carbon double bonds,yielding a chlorine-containing,intrinsically flameretardant bio-plasticizer.When combined with di-(2-ethylhexyl)phthalate(DOP)in PVC formulations,the chlorinated fatty acid methyl ester is qualified as a co-plasticizer while conferring flame retardancy upon the PVC coatings.This approach involves only a one-step procedure that employs renewable fatty acid methyl esters and cheap chlorine gas as raw materials,thus being of great potential to enable intrinsically flame-retardant bioplasticizers on a large scale to manufacture functional PVC artificial materials for application in fire-prone scenarios.

关键词： plasticizer Fatty acid methyl ester Chlorine Polyvinyl chloride Artificial material

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