Materials and Properties
JI Meiyu, ZHAO Yizhe, ZHANG Wenchao, GUO Xiaoyan, YANG Rongjie
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252 )
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A series of epoxy composites with different loadings of 1⁃oxo⁃4⁃hydroxymethyl⁃2，6，7⁃trioxa⁃l⁃phosphabicyclo ［2.2.2］ octane （PEPA） and ammonium polyphosphate （APP） and a fixed loading of montmorillonite （MMT） were prepared to enhance their flame⁃retardancy. The synergistic effect of APP and PEPA on the flame⁃retardant properties of the epoxy composites was evaluated by vertical burning experiment， limiting oxygen index， and cone calorimetry. A smoke density test was also carried out to demonstrate the collaborative smoke suppression effect of APP and PEPA. The experimental results indicated that when 15 wt% of APP/PEPA/MMT at a mass ratio 69/25/6 was incorporated into epoxy resin， the resultant epoxy composite obtained an improvement in limiting oxygen index up to 31.5 % and reached the UL94 V⁃0 rating in the vertical burning test. Moreover， its peak heat release rate （HRR） and total smoke release （TSR） decreased by 73.6 % and 70 %， respectively. Based on the HRR， peak HRR， and TSR results obtained from cone calorimetric measurements， PEPA， APP， and their compounds can generate good flame⁃retardant effectiveness in both gas phase and condensed phase. To understand the synergistic mechanisms about the flame⁃retardant and smoke suppression effects deeply， thermal gravimetric analysis coupled with Fourier⁃transform infrared spectroscopy， visual observation， and scanning electron microscopy were conducted to characterize the gas and condensed phases of epoxy composites containing APP and PEPA flame retardants.
LIN Zhenbin, ZHU Huihao, WANG Yu, XIE Linsheng, LI Guo, MA Yulu
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117 )
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In this study， a thermal conductive light diffusion material with good optical and thermal conduction was prepared by blending polystyrene （PS） and magnesium hydroxide （MH） as an inorganic filler to match the refractive index. The comprehensive performance of the PS/MH thermal conductive light diffusion materials were regulated through adjusting the content of MH and employing the MH with a multi⁃particle size for compounding based on the experimental results obtained from the measurements on their micro⁃morphology， optical properties， thermal conductivity and mechanical properties. The results indicated that there was an MH thermal conductivity network formed in the matrix with an increase in the MH content. The transmittance of the thermal conductive light diffusion materials decreased gradually， their haze increased and tended to be stable， and their thermal conductivity was significantly improved. When 30 wt% MH with a multi⁃particle size content was incorporated， the resultant PS⁃30⁃3 thermal conductive light diffusion material obtained optimal comprehensive performance， its transmittance and haze reached 75.9 % and 92.70 %， respectively， and its thermal conductivity reached 0.52 W/（m·K）， which is 10 times as much as that of pure PS ［0.05 W/（m·K）］.
WEN Wei, GONG Weiguang, MENG Xin
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252 )
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Poly（epoxypropoxy） silsesquioxane （PESQ） was designed and synthesized and then melt blended with poly（glycolic acid） （PGA） at loadings of 0.5 wt%， 1.0 wt%， 2.0 wt% and 4.0 wt% to prepare the hydrolysis⁃resistant crystalline PGA. The changes in the rheological， hydrolysis， and crystallization properties of the PESQ⁃modified PGA was investigated to study the effect of PESQ modification on PGA. The results indicated that a combination of PESQ and PGA in a chain expansion form effectively improved the hydrolytic performance of PGA through increasing its viscosity， resulting in a reduction in the mass loss by 21.1 % after degrading for 10 days. Furthermore， PESQ could facilitate the crystallization of PGA. With an increase in the addition amount of PESQ， the crystallization temperature of the modified PGA increased to 179.5 ℃， which was higher than that of pure PGA by 6.8 ℃. There is a decrease in the initial crystallization activation energy of the modified PGA， indicating that PESQ contributed to heterogenous nucleation.
LYU Zhengyang, QIU Jian, XING Haiping, JIANG Zhiwei, LIU Jie, TANG Tao, LI Sanxi
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126 )
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In this study， a type of high⁃strength and high⁃flame retardant polyphenylene ether （PPO） composite foams was prepared by using syndiotactic polystyrene （sPS） instead of high⁃impact polystyrene （HIPS）， styrene⁃ethylene/butadiene⁃styrene block copolymers （SEBS）， and halogen⁃free flame retardants through supercritical carbon dioxide foaming. The effect of sPS on the mechanical properties， foaming behavior， compressive strength， and flame⁃retardant performance of the composite foams were investigated. The results indicated that the introduction of sPS improved the rigidity and melt viscoelasticity of the composites significantly. The foamability of the composites was enhanced with an increase in the melt viscoelasticity. When 23 wt% sPS was added， the foaming rate of the composites increased from 5.9 to 36 times. The introduction of composite halogen⁃free flame retardants improved the flame⁃retardant performance of composite foams significantly. The PPO/HIPS/sPS composite foam with a density of 0.14 g/cm3 reached a flame⁃retardant grade of the UL94 V⁃0 rating and exhibited a limiting oxygen index of 27.4 vol%. At a density of 0.29 g/cm3， the PPO/HIPS/sPS composite foam containing 23 wt% of sPS presented an increase in the compressive strength from 1.9 MPa to 6.4 MPa.
FANG Xiaotong, SHI Yerong, HU Jing
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122 )
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A free radical photosensitive resin suitable for ultraviolet （UV） cured 3D direct ink writing printing was synthesized using bisphenol⁃A epoxy acrylate （EA） as a prepolymer， 1，6⁃hexanediol diacrylate （HDDA） as a monomer， and 2，4，6⁃trimethylbenzoyl diphenylphosphine oxide （TPO） as an initiator. The resin could form a cross⁃linked network under UV irradiation. The effect of TPO content on the surface drying time， gel rate， and volume shrinkage of photosensitive resin were investigated. The results indicated that when 6 g TPO was added， the surface drying time of the cured resin was the shortest， its gel rate was highest， and its volume shrinkage was largest. According to these results， the effect of the mass ratio of prepolymer to monomer on the surface drying time， viscosity， gel rate， volume shrinkage， and mechanical properties of the photosensitive resin were investigated. The results demonstrated that the photosensitive resin containing 6 g TPO had the shortest surface drying time， lower viscosity， the largest gel rate， and excellent mechanical properties at an EA/HDDA of 20/9. This suggests that the developed photosensitive resin is suitable for use in UV cured 3D direct ink writing printing.
CHEN Yuquan, REN Bin, LI Xuemei, RAO Suhan, GUO Zhangyi, HUANG Ying, KANG Ming, LI Xiuyun
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128 )
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In this study， an intrinsic flame⁃retardant epoxy resin （TA⁃VAN⁃EP） containing a Schiff⁃base structure was prepared by using vanillin （VAN）， tyramine （TA） and epichlorohydrin （ECH） as raw materials. The chemical structure of the resultant TA⁃VAN⁃EP was characterized by Fourier⁃transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy， and its curing behavior， mechanical performance， thermal stability， flame⁃retardant performance， and other important properties were investigated. The results indicated that the synthesized TA⁃VAN⁃EP exhibited a desired structure. Compared to pure epoxy resin， TA⁃VAN⁃EP obtained a significant improvement in the mechanical properties， in which there is an increase in the tensile strength by 82.0 %. Moreover， it also showed an increase in the glass⁃transition temperature from 152 to 190 ℃. In addition， TA⁃VAN⁃EP achieved a UL94 V⁃1 rating in the vertical burning experiment， along with an increase in the limiting oxygen index value from 24.7 % to 28.4 %. Furthermore， TA⁃VAN⁃EP presented a significant reduction in the total heat release， smoke production rate， and total smoke release. Owing to the presence of a dynamic Schiff⁃base structure in its structure， TA⁃VAN⁃EP exhibited good biodegradation performance under acidic conditions.
ZHANG Jiahang, MENG Mengmeng, YANG Jiaxin, LI Yun, ZHANG Yang
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93 )
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In this study， the conductive pressure⁃sensitive adhesive was prepared through multiple solution casting. Chain spherical nickel powders （C⁃Ni）， flake nickel powders （F⁃Ni） and polyaniline （PANI） were incorporated as functional fillers into the resultant acrylic type pressure⁃sensitive adhesive （a⁃PSA）. The results indicated that these fillers were asymmetrically distributed in the thickness direction of the conductive pressure⁃sensitive adhesive due to the effect of gravity. This significantly improved the electrical properties of the resultant composite pressure⁃sensitive adhesive. The a⁃PSA/10 wt% C⁃Ni/1 wt% PANI composite adhesive exhibited the highest conductivity of 0.013 S/m. With increasing the PANI content， there was an increase in the response of the capacitance to bending angle and pressure of the composite adhesives. The most sensitive response to bending angle was observed for the composite adhesives containing 1 wt% PANI. At a pressure of 12.5 kPa， the change rate of capacitance of the composite adhesive reached 1.83. Its tensile strength was 2.88 times as much as that of the a⁃PSA， whereas its adhesion strength decreased with an increase in the filler content. The a⁃PSA/10 wt%C⁃Ni/1 wt% PANI composite adhesive exhibited the best comprehensive performance.
HU Jiaai, ZHANG Yiqing, XU Jiahe, LI Qiaoli, FENG Xixi, XU Xuan, LI Xinao, NI Tianheng, HOU Lianlong, MA Haikun, SUN Guohua
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181 )
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Polyimide （PI）/hydroxyethyl cellulose （HEC） nanofiber composite membranes were prepared via in⁃situ integrated reinforcement modification using HEC as a functional modification material for PI nanofiber membranes. The strength of PI nanofibers membrane was increased due to the bonding and coating of the PI nanofibers with HEC， and the polar functional groups of HEC were uniformly distributed on the surface of PI nanofibers to act as functional sites for realizing the regulation of lithium⁃ion flow. The results indicated that the introduction of HEC could endow the PI/HEC membranes with excellent tensile strength of 58.65 MPa， high wettability along with a contact angle of 14.31°， a high ion conductivity of 1.63 mS/cm， and a high lithium⁃ion transfer number of 0.58. The battery equipped with the PI/HEC composite membranes showed high discharge capacities of 170.1 and 135 mAh/g at 0.1 C and 2 C， respectively， a capacity retention rate of 69.43 % after 100 cycles at 1 C， and a Coulomb efficiency of nearly 100 %. In addition， the results from the lithium deposition test at 1 mA/cm2 indicated the potential of the battery was lower than 0.23 V after 600 h. The density function theory calculation results indicated that HEC has a higher binding energy for lithium ions， confirming that the functional site of HEC can regulate lithium ions to inhibit lithium dendrites.
WANG Jun, GE Yuan, CAO Anran, ZHANG Shoulei, YAN Zetong
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137 )
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Thermal oxidative stabilized （TOS） fibers with different pre⁃oxidation degrees were prepared by using constant draft polyacrylonitrile （PAN） fibers under air atmosphere according to the pre⁃oxidation degree obtained from the relative cyclization rate determined by Fourier⁃transform infrared spectroscopy. The effect of pre⁃oxidation degree on the chemical and crystal structures， microstructure， and mechanical properties of the resultant TOS fibers were investigated. The results indicated that the conjugated carbonyl groups began to form at a pre⁃oxidation degree greater than 54.7 % and tended to increase gradually. The TOS fibers exhibited new diffuse peaks and ordered structures at a pre⁃oxidation degree of 83.2 %， and their cross section presented an obvious radial non⁃uniform structure， so⁃called “skin⁃core structure” along with a decrease in the elongation at break. Therefore， the TOS fibers obtained a cyclization degree of 72 %， thus resulting in fewer structural defects and better performance.
LI Youshuang, JIN Qiushuo, TANG Jingyue, JIA Meng, XU Bo
Abstract (
124 )
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In this study， DOPO⁃DBA⁃F as a flame⁃retardant cross⁃linking agent was introduced into the bismaleimide resin as a raw material to prepare a modified material with both self⁃healing and flame⁃retardant properties. The structure and performance of the modified material was characterized by using Fourier⁃transform infrared spectroscopy， thermogravimetry analysis， differential scanning calorimetry （DSC）， polarized light microscopy， limiting oxygen index meter， vertical burning experiment， and cone calorimetry. The morphology of the residual char was observed by scanning electron microscopy. The results indicated that the formation of reversible Diels⁃Alder （DA） bonds effectively improved the recyclability of the bismaleimide resin. The presence of the reversible DA bonds between the furan groups and bismaleimide resin was confirmed by DSC. Meanwhile， the introduction of flame⁃retardant cross⁃linking agent successfully improved the flame⁃retardant properties of the modified material， resulting in a limiting oxygen index of 38.5 % and a UL94 V⁃0 rating in the vertical burning experiment.
WANG Aohua, DUN Dongxing, MENG Ruijing, ZHANG Yuxia
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108 )
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In this study， diphenylhydrazide sebacic acid （ST⁃NAB3） was used to regulate the properties of a chemical graft product （C⁃PLA） obtained from the chain⁃extension modification of polylactic acid （PLA） using styrene⁃acrylonitrile⁃glycidyl methacrylate （SAG） a chain extender. Then， C⁃PLA⁃ST⁃NAB3 foams were prepared by using supercritical CO2， and their crystallization performance， thermal performance， rheological behavior， foaming properties， and microstructure were investigated by polarization light microscopy， differential scanning calorimetry， rotational rheometer， and scanning electron microscopy. The results indicated that the addition of ST⁃NAB3 increased the crystallization rate of C⁃PLA foams significantly， resulting in a reduction in the crystal size but an increase in the crystal density. With an increase in the ST⁃NAB3 content， the crystallinity degree of the C⁃PLA foam increased from 3.2 % to 20.2 %. When the content of ST⁃NAB3 was 0.3 and 0.4 wt%， the C⁃PLA⁃ST⁃NAB3 foams with a uniform cell size could be formed at different foaming temperature.
Processing and Application
ZHANG Liyan, DU Xiangyu, DING Yumei, YANG Weimin, JIAO Zhiwei, HE Wei
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90 )
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Based on the torsional micro⁃nano stacking method with the state proprietary intellectual property rights， the dispersive regulation of inorganic particles by micro⁃nano stacking units was analyzed using a particle tracer technology， and it was compared with the twin⁃screw mixing effect under the same flow field. The results indicated that the micro⁃nano laminated element used in this study had a strong shear stress in the flow channel because of its unique torsional structure. Under the same conditions， the average shear stress was dozens of times as much as that of the twin⁃screw mixing. The outlet particle size of the micro⁃nano laminated unit had a larger proportion in the small size area， and its peak density was 0.09， which was 0.07 higher than that of the twin⁃screw mixing. Based on these characterization results， the used micro⁃nano stacked units exhibited a strong ability to disperse and regulate inorganic particles， resulting in better dispersion and mixing of particles in the polymer matrix. The mixing effect of inorganic particles and polymer melt by micro⁃nano lamination device was also verified.
XU Jiawei, ZHU Jingxian, HUO Zejun, GAO Qiang, KANG Tingting, KANG Xiaoya, ZHUANG Jian
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182 )
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In order to improve the production efficiency of polymer microneedles and molding quality， reduce the production cost， and meet the requirement of mass production， a micro injection molding technology was used to prepare the poly（lactic acid） （PLA）⁃based medical and aesthetic microneedle patches. The effects of melt temperature， mold temperature， injection speed， holding pressure， and holding time on the tip diameter of the resultant PLA⁃based microneedles were investigated by an orthogonal experiment， and their morphology， size and mechanical strength were characterized by electron microscopy and dynamometry. Moreover， the skin penetration and penetration experiments in vitro were carried out to verify the penetration and penetration effects of the PLA microneedles. The results indicated that the injection⁃molded PLA microneedles obtained a good molding effect with a minimum tip diameter when the process parameters were set to a melt temperature of 200 ℃， a mold temperature of 45 ℃， an injection speed of 360 mm/s， a holding pressure of 50 MPa， and a holding time of 4 s. Under such a condition， the PLA microneedles achieved a height of 0.524 mm and a tip diameter of 0.027 mm. The needle tip molding was obviously optimal， and the developed microneedles could meet a requirement of performance.
SONG Zeming, WAN Jiancheng, HAO Yujing, WANG Fan, ZHOU Wei, PENG Fei
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138 )
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Continuous carbon⁃fiber⁃reinforced polyamide 6 prepreg was used to prepare a composite pull rod through a winding⁃molding process. The tensile properties of the composite pull rod were evaluated by using a self⁃made tensile tool， and its failure mode and failure mechanism were studied. The results indicated that increasing the molding pressure could reduce the pores in the composite as well as the internal defects， make the structure more compact， and improve the tensile strength of the pull rod. The composite pull rod without a collar showed a tensile failure position at its end， and the outer fiber was pulled and split. Only the inner fiber worked until it was pulled and broken. In this case， the tensile strength was low. The composite pull rod with a collar showed a tensile failure position close to the shaft sleeve on the side. The fiber was broken， and the fracture section was relatively flush. During the whole tensile process， the transverse restraint of the collar enabled all fibers to play a good tensile role， resulting in higher tensile strength.
XIAO Bing, LIU Biao, CHEN Tianrong, JI Haibo, DENG Xiaozhen, XU Fang, ZENG Jiahang
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106 )
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In this study， the traditional micro⁃coextrusion and gas⁃assisted micro⁃coextrusion flow models were established for double⁃layered microtubules. The effects of zero shear viscosity （）， relaxation time （）， and material parameters and on the die swell rate were investigated by using a numerical simulation technology. The results indicated that the die swell rate was greatly affected by and in the traditional micro⁃coextrusion process. With an increase in the outer melt viscosity， the die swell rate increased from 29.15 % to 43.77 % and then tended to be stable. The die swell rate was less affected by and ， and it decreased slightly with an increase in and . The die swell rate varied between 37 % and 39 %. However， in the gas assisted co⁃extrusion process， the die swell rate always approached zero when ，， and changed， and there was no obvious swelling or deformation phenomenon.
WANG Ye, LIU Yi
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130 )
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In this study， different injection molding methods were adopted to prepare the test samples of polypropylene （PP） transparent material for the measurement of fog degree. The key factors affecting the fog degree of the transparent material， such as injection pressure， injection speed， melt temperature， and pressure holding pressure were investigated. The optimal process parameters for preparing the test samples for fog degree were determined to be an injection pressure of 55.52 MPa， an injection rate of 40 mm/s， a melt temperature of 200 ℃， a mold temperature of 40 ℃， and a holding pressure of 48.58 MPa.
Additive
DU Jiaying, XIN Fei, HU Jiayue, FENG Kaixuan
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Graphitic carbon nitride （g⁃C3N4） is a carbon⁃nitrogen compound that can be used to improve the flame⁃retardant properties of polymer materials. In this paper， the research progress in the flame⁃retardant polymer systems based on g⁃C3N4， including flame⁃retardant systems with and without metal elements， was reviewed， and their flame⁃retardant mechanism and the role of g⁃C3N4 in the flame⁃retardant system were analyzed.
XU Zhun, JIA Meng, SHAN Hao, XU Bo
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120 )
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To inhibit the exothermic situation of polyamide 6 （PA6） during combustion， furan groups that can char at high temperature were introduced into flame retardants. A series of flame retardants containing furan groups were designed and synthesized， and their flame⁃retardant and heat⁃inhibition properties as well as corresponding mechanisms were investigated by means of limiting oxygen index， vertical combustion experiment， and cone calorimetry. The results indicated that the furan groups could generate different heat suppression effects under different external environments and internal morphologies. The PA6 compounds containing large⁃molecule flame retardants exhibited a better heat suppression effect than those with small⁃molecule flame retardants according to the cone calorimetric test results.
Machinery and Mould
CHU Zhong, ZHAO Caoxi, KANG Hui, NI Zihan, LI Zhitong, ZHANG Jicong
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92 )
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Taking a certain spray cosmetic cap as an object， a lattice structure was designed on the top of the mold core based on the design of the conformal cooling channel of mold core. A simulation was carried out with the help of the Moldex and Ansys software to analyze the temperature distribution on the surface of the mold core as well as the stress situation. Futhermore， the experimental validation was also performed on the mold core parts manufactured by selective laser melting. The results indicated that the resultant lattice structure exhibited good heat transfer performance and improved the problem in the uneven temperature distribution significantly. The surface of the core presented a homogenous temperature distribution， and its surface temperature difference was improved by 78 %. The strength of the core of the mold with the added lattice structure could meet a requirement of practical use.
YE Xianzhen, RONG Xing, CAI Bulin, ZHANG Weili
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112 )
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In the bi⁃color injection molding process， the first shot of the base plastic part remains on the movable mold side and moves with the movable mold to the stationary mold side of the second shot for a mold closing to complete the second shot of encapsulation molding. To address the issue of encapsulation molding on the back of the base plastic part with a side on the movable mold， it is necessary to replace the corresponding insert of the movable mold. To this end， through controlling the sequence of opening and closing actions of the mold， the movable mold slider and insert were moved together by a bent pin fixed on the stationary mold side of the first shot to obtain a replacement action between different inserts of the first and second shots. Then， the extension and retraction of the insert were controlled by limit blocks and return springs. To prevent the base plastic part from adhering to the stationary mold cavity during mold opening， a nitrogen spring⁃driven ejection mechanism for the base plastic part was designed on the stationary mold side of the first shot. To ensure the safe， accurate， and reliable operation of the automatic replacement of inserts， ejection， and other mechanisms， the corresponding safety mechanisms were designed.
Review
WANG Xiang
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Graphene has attracted extensive attention due to its unique structure and excellent properties. Graphene has achieved industrialization； however， it has not yet gained large⁃scale applications by now. This may be due to the fact that the properties and cost of the graphene obtained from large⁃scale production are difficult to meet a requirement of the practical applications. The development of green， low⁃cost， and high⁃quality graphene is still necessary. As the most easily achievable supercritical fluid， supercritical CO2， exhibits a number of advantages for the preparation of graphene， such as high product quality， short preparation time， environmental friendliness， low cost， and suitability for large⁃scale production. This review summarized the main research processes in the preparation of graphene through supercritical CO2 exfoliation in recent years and introduced the corresponding product quality of the resultant graphene. The prospects for future research in the large⁃scale preparation of graphene were also discussed.
ZHANG Lurong, HU Qing, ZHAO Biao, PAN Kai
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Polyamide is the most widely used engineering plastic with excellent comprehensive properties； however， it has a flammable nature. Therefore， a flame⁃retardant modification is needed for broadening its application range. This paper reviewed the research progress in the copolymerization type of flame⁃retardant polyamide， in which the molecular structure of reactive flame⁃retardant moiety， flame⁃retardant mechanism， and flame⁃retardant performance were introduced in detail. Finally， the current challenges and development prospects in the field of copolymerization type of flame⁃retardant polyamide were analyzed.
ZHANG Cheng, XIE Jikai, GUO Jiaxing, HAO Zhi, LUO Zhu, CHEN Yulin
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252 )
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This paper reviewed the research progress in modification of polytetrafluoroethylene （PTFE） in recent years. The advantages and disadvantages of surface modification， blending modification and filling modification methods for the modification of PTFE were summarized. Meanwhile， the effect of modification method on the properties of PTFE were analyzed. Finally， the development trend in the field of PTFE modification was prospected.
MU Minhao, LIU Zhihai, ZHENG Mingming, GUO Zengxian, WEI Hao, WANG Guojun
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183 )
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Aiming at the oil absorption mechanism of resin⁃based absorption materials， this paper reviewed the research progress and development trend in resin⁃based foams and acrylic resins as oil absorption materials in recent years. In addition， the problems currently existing in the research were summarized， and the future development trend for the oil absorption materials was prospected.
