酪素基rGO复合乳液的制备及其阻燃性能

为制备具有增强阻燃效果的皮革涂饰材料,首先以天然石墨为原料,采用Hummers法制备氧化石墨烯(GO),并采用NaBH4对其进行还原得到还原氧化石墨烯(rGO).通过FTIR,XRD和TEM等对其进行表征.结果表明,成功制备了rGO纳米材料.随后,采用物理共混法将rGO引入天然蛋白质酪素体系,制备酪素基rGO复合乳液并将其应用于皮革涂饰,对涂饰后革样的阻燃性能、力学性能和耐干湿擦性能进行测试.结果表明,当rGO的含量为酪素体系溶质质量的0.5％时,与未含rGO的酪素体系相比,涂饰后革样的燃烧速率下降47.2％,极限氧指数(LOI)由24.2％增加至26.3％,热释放速率(HRR)下降53.1％,总热释放速率(THR)也有所降低.rGO的引入对涂饰后革样的力学性能和耐干湿擦性能影响不大.     

层层组装法制备抗菌-阻燃型生物质基复合涂层

为了赋予皮革更多功能，提高其使用价值，以己内酰胺（CPL）改性酪素（CA）（记为CPL-CA）、壳聚糖（CS）及植酸（PA）生物质材料为原料，引入无机组分氢氧化镁（MH），采用层层组装（LBL）技术在皮革上构筑具有阻燃及抗菌性能的涂层。对构筑涂层的革样进行了FTIR、SEM及EDS表征，并对其进行了抗菌性能及阻燃性能测试。结果表明，CS的引入明显改善了涂层的抗菌性，当CS溶液质量分数为1.0%时，涂层对金黄色葡萄球菌有良好的抑菌效果。固定CPL-CA溶液，在CS溶液质量分数为1.0%、浸渍层数3层的条件下，由质量分数为1.5%MH溶液和体积分数为0.4%PA溶液制得的复合溶液构筑涂层的革样的热释放速率（HRR）峰值和热释放总量（THR）分别比未浸渍革样降低了42.31%和40.97%，表明成功制备了具有良好抗菌及阻燃性能的生物质基复合涂层。     

缓香型玉米醇溶蛋白微胶囊乳液的制备及应用

为改善皮革的特殊气味并提升其应用性能,该研究以玉米醇溶蛋白（Zein）、艾叶香精（AAE）以及普兰尼克F127等为原料,通过反溶剂法制备缓香型玉米醇溶蛋白微胶囊（AAE@ZMs）乳液,再将AAE@ZMs乳液与成膜剂己内酰胺改性酪素复配后应用于皮革涂饰。结果表明,Zein与F127、AAE和戊二醛通过化学交联和氢键相互作用,同时F127和AAE可使Zein中的氨基酸重排并发生荧光猝灭;制得的AAE@ZMs乳液中微胶囊平均粒径约为298.6 nm且具有较好的分散性和稳定性;AAE@ZMs的包覆率和负载率分别可以达到73.2%和5.8%,在良溶剂中释放120 h时的AAE累积释放率约为83.1%。将AAE@ZMs应用于皮革涂饰后,涂饰革样中AAE的释放周期为6周,对金黄色葡萄球菌和大肠杆菌均具有较好的抑制效果,同时涂饰革样还展现出较好的机械性能。     

碱溶性聚(丙烯酸丁酯/丙烯酸)的合成及性能

合成了碱溶性聚(丙烯酸丁酯/丙烯酸)〔P(BA/AA)〕,探讨了丙烯酸用量及不同引发体系对其表面张力、离心稳定性和乳化性的影响,对其结构进行了表征。傅里叶红外光谱(FTIR)分析表明,P(BA/AA)中无C C存在,聚合完全;差示扫描量热(DSC)分析表明,共聚物的玻璃化转变温度(Tg)为21.3℃;透射电镜(TEM)测定了P(BA/AA)的平均粒径小于100 nm,粒径分布均匀。以该共聚物为表面活性剂与丙烯酸酯类进行乳液聚合制备了皮革涂饰剂,应用于皮革涂饰后,革样的物理机械性能较采用常规乳化剂制备的丙烯酸树脂涂饰革样抗水性提高了28.08%,透气性提高了18.5%,耐湿擦性提高了半级,耐折牢度无明显变化。     

一种新型改性丙然酸树脂的制备

在以丙烯酸酯类衍生物为主组分的聚合体系中加入醋酸乙烯、苯乙烯、甲基丙烯酸等作为改性剂，制得粘结力强、耐温度变化好、耐干湿擦及耐有机溶剂的新型改性丙烯酸树脂皮革涂饰剂。产品综合应用性能优于目前通用的几种皮革涂饰剂。生产工艺技术已应用于５００ｔ／ａ的工业装置中。     

BiVO4/rGO复合物的制备及其 光催化还原CO2研究

采用水热法制备了颗粒状单斜相钒酸铋（BiVO4）/还原氧化石墨烯（rGO）复合催化剂。采用傅里叶红外光谱、拉曼光谱、X射线衍射和紫外-可见漫反射光谱对合成的复合材料做了表征。采用透射电镜、扫描电镜和氮吸附脱附实验对复合材料的表面形貌和表面积做了分析测试。实验结果表明,BiVO4复合物能选择性将CO2还原成甲醇,石墨烯的引入能很好地改善BiVO4光催化还原CO2的性能。当石墨烯的加入量为3%（质量分数）时,在氙灯功率为600 W的条件下,光照6 h后,BiVO4/rGO复合材料光催化还原CO2生成的甲醇产量达到513.1 μmol/L,比相同形貌的纯BiVO4的甲醇产量高73.6%。     

功能化石墨烯改性双马来酰亚胺复合材料的微观表征及性能

采用改进Hummers法制备氧化石墨烯（GO）,分别采用水合肼、壳聚糖、KOH还原得到了还原氧化石墨烯（rGO）并对三种还原方法做了对比,选择最佳方案;再通过离子液体（NH₂IL）对rGO功能化得到改性还原氧化石墨烯（NH₂IL-rGO）。以二烯丙基双酚A （BBA）和双酚A双烯丙基醚（BBE）为活性稀释剂,4,4'-二氨基二苯甲烷型双马来酰亚胺（MBMI）为反应单体,制备了MBMI-BBA-BBE （MBAE）树脂基体;同时以NH₂IL-rGO为增强体采用原位聚合法制备NH₂IL-rGO/MBAE复合材料。表征了石墨烯和复合材料的微观形貌并分析了石墨烯对复合材料性能的影响。结果表明：NH₂IL-rGO在树脂基体中以两相形式存在,结构完整,并赋予复合材料优异的性能。当NH₂IL-rGO含量为2%（质量）时,复合材料冲击强度和弯曲强度最大,分别为15.33 kJ/m²和142 MPa,热分解温度为435.73℃、当测试频率为100 Hz～10 kHz时介电常数发生突变达到84。     

缓香型玉米醇溶蛋白微胶囊乳液的制备及应用

为改善皮革的特殊气味并提升其应用性能,以玉米醇溶蛋白(Zein)、艾叶香精(AAE)以及普兰尼克F127等为原料,通过反溶剂法制备缓香型玉米醇溶蛋白微胶囊(AAE@ZMs)乳液,再将AAE@ZMs乳液与成膜剂己内酰胺改性酪素复配后应用于皮革涂饰.结果表明,Zein与F127、AAE和戊二醛通过化学交联和氢键相互作用,同时F127和AAE可使Zein中的氨基酸重排并发生荧光猝灭.当Zein和AAE质量分别为0.1 g和0.01 g时,制得的AAE@ZMs乳液中微胶囊平均粒径约为298.6 nm,且具有较好的分散性和稳定性,AAE@ZMs对香精的包覆率和负载率分别可以达到73.2％和5.8％,微胶囊中的AAE在良溶剂中释放120 h后的累积释放率约为83.1％.将复配后的AAE@ZMs乳液应用于皮革涂饰后,涂饰革样中AAE的释放周期为6周,对金黄色葡萄球菌和大肠杆菌均具有较好的抑制效果,同时涂饰革样还展现出较好的机械性能.     

用乳化法制备石墨烯/三元乙丙橡胶复合材料

在氧化石墨烯（GO）存在下,采用溶液-乳化技术制备得到GO/三元乙丙橡胶（EPDM）胶乳,减压蒸馏后加入水合肼原位还原胶乳中的GO,从而得到还原氧化石墨烯（rGO）/EPDM胶乳。复合胶乳经絮凝后进行热压和硫化,最后得到rGO/EPDM复合材料。结果表明,随着乳化的进行,由于EPDM接枝的马来酸酐与GO之间的强相互作用,GO可以自组装吸附到EPDM乳胶颗粒表面,并且在还原过程中rGO没有发生明显的团聚。在制备的rGO/EPDM复合材料中,rGO在整个EPDM基质中均匀分散,并明显提高了EPDM的热导率。     

纳米二氧化钛/石墨烯改性水性聚氨酯抗菌涂料的制备与评价

通过简单高效的方法制备纳米二氧化钛 /还原氧化石墨烯（ TiO₂/rGO）复合材料,对复合材料进行红外光谱（ FT-IR）、扫描电镜（ SEM）以及 X射线衍射（XRD）表征,结果表明：成功制备了氧化石墨烯、锐钛型纳米 TiO₂,并将纳米 TiO₂均匀负载于氧化石墨烯片层,经水热还原得到 TiO₂/rGO复合材料。将制备的 TiO₂/rGO复合材料添加到水性聚氨酯涂料中,制备涂膜并测定其光催化降解能力,结果表明：纳米 TiO₂/rGO填料复合的聚氨酯涂膜具有较高的光催化能力。依据 HG/T 3950—2007标准测定涂膜抗菌性能,结果表明：水性聚氨酯涂料的抗菌能力达到国家 Ⅰ级标准,可以有效替代有机抗菌剂。该环保复合涂料在物理性质和应用性能上均符合化工行业标准要求。     

Graphene/carbon black/natural rubber composites prepared by a wet compounding and latex mixing process

The extensively used latex mixing approach to prepare graphene can improve the graphene dispersion but meets some challenges in the preparation of high content carbon black filled rubber system like a rubber tire. Owing to the high melt viscosity of the rubber/graphene masterbatch, the dispersion of carbon black is not perfect during twin-roll mixing and some aggregates will be formed. Here we proposed a wet compounding process, combined with ultrasonically assisted latex mixing, named as the WCL method to prepare reduced graphene oxide/carbon black/natural rubber (rGO/CB/NR) composites. The morphological observations confirmed that both graphene and carbon black can be evenly dispersed in the rubber composites. The incorporation of rGO also improves the hardness, thermal conductivity and anti-aging properties of the composites. The rGO/CB/NR composites prepared by the WCL method possess better mechanical properties compared to conventional latex mixing. The entanglement-bound rubber tube model was utilised to understand the reinforcing mechanism.     

Preparation of Ag/reduced graphene oxide reinforced copper matrix composites through spark plasma sintering: An investigation of microstructure and mechanical properties

The reduced graphene oxide (rGO) decorated with Ag nanoparticles was synthesized by the chemical reduction of graphene oxide in an aqueous solution containing AgNO₃, in the presence of hydrazine hydrate as a reducing agent. The reduction of graphene oxide was confirmed by FT-IR and raman spectroscopy analyses. The x-ray diffraction pattern and UV–visible investigations demonstrated the formation of Ag particles on the surface of rGO sheets. After successful decoration, the Ag/rGO nano-composite was used as the reinforcement in the copper matrix composite. Cu–Ag/rGO composites with different percentages of Ag/rGO (0.4, 0.8, 1.6 and 3.2 vol%.) were prepared by mechanical milling and spark plasma sintering (SPS). The effects of the Ag/rGO content on the consolidation process, micro-hardness, bending strength and also, fracture surface of the prepared samples were then investigated. The three-point bending strength of the sintered samples was increased from 285 to 472 MPa by the addition 0.8 vol%. of Ag/rGO, as compared to the pure Cu. Moreover, increasing the reinforcement content to the 3.2 vol%. Ag/rGO led to decreasing the bending strength to 433 MPa. The highest micro-hardness (81 Hv) was obtained for the composite sample containing the 1.6 vol%. Ag/rGO. By increasing Ag/r-GO as the reinforcement (3.2 vol%.), the Vickers hardness was decreased to 69 Hv. Also, investigation of the fracture surface morphology showed transformation of fracture mechanism from plastic changes to brittle ones by raising the Ag/rGO content volume from 0.8 to 1.6 vol %.     

Preparation of well‐dispersed reduced graphene oxide and its mechanical reinforcement in polyvinyl alcohol fibre

The current work reports the preparation and characterization of polyvinyl alcohol (PVA) composite fibres reinforced with graphene reduced from graphene oxide (GO) by using oligomeric proanthocyanidin (OPC) as a reductant. After reduction, most of the oxygen‐containing groups were removed from the GO and reduced graphene oxide (rGO) was prepared. As a result of combined OPC as a dispersant, rGO could be well dispersed in a dimethyl sulfoxide/H₂O mixed solvent and in PVA matrix, and the PVA/rGO dispersion was wet spun followed by hot drawing to prepare continuous PVA/rGO composite fibres. The PVA/rGO composite fibres exhibited a significant enhancement of mechanical properties at low rGO loadings; in particular the tensile strength and Young's modulus of the 2.0 wt% rGO and PVA composite fibre increased to 244% and 294% respectively relative to neat PVA fibre. Moreover, the storage modulus (?10 °C) and T_g increased to 300% and 7.2 °C, respectively. © 2016 Society of Chemical Industry     

Synthesis and application of hyperbranched poly(urethane‐urea) finishing agent with amino groups

The isocyanate‐terminated linear polyurethane prepolymer (LPPU) was successfully synthesized via step‐by‐step polymerization, with isophorone disocyanate (IPDI) and polytetramethylene ether glycol (PTMG, M_n = 2000 g/mol) used as raw materials, dibutyltin dilaurate (DBTDL) as the catalyst, 1,4‐butanediol (BDO) as the chain extender and anhydrous ethanol (EtOH) as the blocking agent. Then the hyperbranched poly (urethane‐urea) (HBPU) containing amino groups was synthesized by grafting LPPU on amino‐terminated hyperbranched polymers (NH₂‐HBP). The molecular structure of LPPU and HBPU were characterized by means of FT‐IR and ¹H‐NMR. It was founded that LPPU and HBPU were successfully synthesized as anticipated. The thermal stability and crystalline morphology of LPPU and HBPU were characterized and analyzed by TG and XRD. Additionally, it was also found that, after addition of 10% HBPU, the water absorption rate, water vapor transmission rate, and water vapor permeability increased markedly by 162.02%, 400.00%, 260.00%, respectively. The tensile strength of membrane decreased by 24.57% and the elongation at break increased by 26.92%. Compared with the leather finished by commercial PU finishing agent, the leather finished by HBPU presented better properties. The water vapor permeability of the leather finished by increased by 13.0%, and the dry‐ and wet‐rub resistances and the physical and mechanical performances were excellent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44139.     

Nano-scale core–shell structural casein based coating latex: Synthesis,characterization and its biodegradability

Nano-scale core–shell type particle of caprolactam-butylacrylate co-modified casein (CA-CPL-BA) bearing poly(butylacrylate) core and casein-caprolactam shell was synthesized via emulsifier-free polymerization, and was applied as the film-former in leather finishing. By utilizing potassium persulfate–sodium hydrogensulfite as a redox pair during preparing CA-CPL-BA, the grafting extent was superior to that initiated by ammonium persulfate–sodium hydrogensulfite, potassium persulfate or ammonium persulfate. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis results demonstrated that the average size of neat casein particle was around 700 nm while the resultant CA-CPL-BA latex particles were significantly decreased to about 80 nm in size. Compared with those of neat casein films, enhanced hydrophobicity and higher thermo-stability of the CA-CPL-BA latex film were confirmed by contact angle test and thermal gravimetric (TG) measurement, respectively. Meanwhile, the application performance of the leather samples finished by CA-CPL-BA was proved to be equivalent to that finished by the commercial leather finishing agent product. A possible mechanism of emulsifier-free polymerization for this system was proposed and then proved. Biodegradability tested by soil burial degradation experiments proved that CA-CPL-BA had preferable biodegradability.     

Proanthocyanidin‐Induced Horizontal Arrangement in Poly(vinyl alcohol)/Graphene Composites with Enhanced Mechanical Properties

A green approach is employed to prepare mechanically enhanced composites by adding noncovalently proanthocyanidin (PC)‐modified graphene (PC‐rGO) into poly(vinyl alcohol) (PVA). Ascorbic acid (AA) is used as the reducing agent, and PC is used as a dispersant to synthesize low‐defect and fully dispersed graphene. After static treatment, the PC‐rGO sheets in the composite form a horizontally arranged structure. Compared with neat PVA, the Young's modulus of the graphene‐modified composites is significantly enhanced by approximately 79.3% with incorporation of 0.9 wt% PC‐rGO. The composites incorporated with GO or AA‐rGO (without PC) have randomly distributed GO structures and apparent rGO agglomeration, resulting in a weaker mechanical property. The dispersibility, degree of defects, distribution state of graphene, and interactions with the polymer matrix are directly related to the final mechanical performance. This new approach to mechanically enhance graphene‐embedded PVA composites provides the possibility for large‐scale production of graphene‐reinforced composite materials.     

皮革黑LR-N染色性能及染色工艺的研究

本文利用色度色差分析及紫外可见吸收光谱等研究了非偶氮皮革专用新型染料一皮革黑LR-N的 染色性能。结果表明,皮革黑LR-N渗透性好,所染皮革黑度好,耐干/湿摩擦牢度高,适于正面革及轻涂 饰革的染色,本文还制定了单独用皮革黑LN-R染黑色革的工艺。     

Synthesis and failure behavior of super-aligned carbon nanotube film wrapped graphene fibers

Significant progress has been made in recent years in research on wet spinning and hydrothermal synthesis of graphene fibers. In this paper, we report the relationship between the mechanical performance of graphene oxide (GO) fibers and their processing parameters in wet spinning. With super-aligned carbon nanotube (CNT) film wrapping, the specific strength and electrical conductivity of reduced GO (rGO) fibers were simultaneously enhanced by 22% and 49%, respectively. Thicker CNT film wrapping of the rGO fiber induces a core–sheath structure; the resulting interfacial debonding and slippage under fiber axial loading were examined. The findings of this study provide guidelines for optimization of high-performance graphene/CNT hybrid fibers.     

聚偏氟乙烯/石墨烯复合材料的制备及性能研究

用溶液共混法制备出聚偏氟乙烯/氧化石墨烯复合材料(PVDF/GO),经高温热压将GO还原得到聚偏氟乙烯/还原氧化石墨烯复合材料(PVDF/rGO)。研究了填料种类及含量对复合材料电学性能、热稳定性和力学性能的影响。结果表明：随GO和rGO的添加,两种复合材料的介电常数(ε _r)均变大、介电损耗(tanδ)变化不大;低含量下GO和rGO均能提高PVDF的热稳定性,但rGO对PVDF性能的改善效果更好;随填料含量从0增加到8%(质量),100 Hz下PVDF/rGO复合材料的ε _r从3.60增加到38.30,PVDF/rGO[4%(质量)]复合材料失重率为5%的分解温度较纯PVDF提高了6.44℃。rGO增强了PVDF的刚性,PVDF/rGO复合材料的拉伸强度先增大后减小,杨氏模量逐渐增大,当rGO含量为4%(质量)时拉伸强度最大,拉伸强度和弹性模量分别较纯PVDF提高了35.30%、22.58%。但GO和rGO都降低了复合材料的击穿场强。