Loading [MathJax]/jax/output/SVG/jax.js

石墨烯桥联的ZnO/Ag3PO4复合材料的制备及其对环丙沙星的降解性能

杜春艳, 宋佳豪, 谭诗杨, 阳露, 张卓, 余关龙

杜春艳, 宋佳豪, 谭诗杨, 等. 石墨烯桥联的ZnO/Ag3PO4复合材料的制备及其对环丙沙星的降解性能[J]. 复合材料学报, 2021, 38(7): 2254-2264. DOI: 10.13801/j.cnki.fhclxb.20200909.001
引用本文: 杜春艳, 宋佳豪, 谭诗杨, 等. 石墨烯桥联的ZnO/Ag3PO4复合材料的制备及其对环丙沙星的降解性能[J]. 复合材料学报, 2021, 38(7): 2254-2264. DOI: 10.13801/j.cnki.fhclxb.20200909.001
DU Chunyan, SONG Jiahao, TAN Shiyang, et al. Preparation of graphene bridged ZnO/Ag3PO4 composite and its degradation performance for ciprofloxacin[J]. Acta Materiae Compositae Sinica, 2021, 38(7): 2254-2264. DOI: 10.13801/j.cnki.fhclxb.20200909.001
Citation: DU Chunyan, SONG Jiahao, TAN Shiyang, et al. Preparation of graphene bridged ZnO/Ag3PO4 composite and its degradation performance for ciprofloxacin[J]. Acta Materiae Compositae Sinica, 2021, 38(7): 2254-2264. DOI: 10.13801/j.cnki.fhclxb.20200909.001

石墨烯桥联的ZnO/Ag3PO4复合材料的制备及其对环丙沙星的降解性能

基金项目: 湖南省教育厅科学研究项目(18B127;19A032;16C0060);国家自然科学基金(51109016)
详细信息
    通讯作者:

    杜春艳,博士,讲师,硕士生导师,研究方向为水处理新材料 E-mail:cydu@csust.edu.cn

  • 中图分类号: TB333

Preparation of graphene bridged ZnO/Ag3PO4 composite and its degradation performance for ciprofloxacin

  • 摘要: 采用沉淀沉积法制备了石墨烯桥联的ZnO/Ag3PO4复合光催化材料,具有优异的可见光催化性能,通过XRD、XPS、SEM、EDS、BET、FTIR、UV-Vis DRS、PL及ESR等表征手段对其晶体结构、形貌、光学性质等进行了表征及分析,并研究了不同氧化石墨烯比例的GO-ZnO/Ag3PO4复合材料对模拟抗生素废水环丙沙星(CIP)的光催化降解性能。由于GO及ZnO的引入,不仅增强了GO-ZnO/Ag3PO4对可见光吸收,且拥有了更高的电子-空穴对的分离效率。当GO与Ag3PO4的质量比为1%时,GO-ZnO/Ag3PO4显示出最佳的光催化活性,60 min可见光照后对CIP降解率可达85.3%。捕获实验表明,超氧自由基(·O2)是反应过程中的主要活性物质,ZnO与Ag3PO4之间形成了异质结,符合Z型电子转移机制,GO的引入进一步提高了电子的快速转移,并使Z型体系更加稳定。经过6次光催化循环,降解率依然保持在70%以上,表明GO-ZnO/Ag3PO4复合材料具有优异的稳定性。
    Abstract: Graphene-bridged ZnO/Ag3PO4 composite photocatalytic material, with excellent visible light catalytic performance, was prepared with the method of precipitation and deposition. Some characterization methods, includingXRD, XPS, SEM, EDS, BET, FTIR, UV-Vis DRS, PLand ESR were adopted to characterize and analyze the crystal structure, morphology, and optical properties of ZnO/Ag3PO4 composite photocatalytic material. Meanwhile, the photocatalytic degradation performance of GO-ZnO/Ag3PO4 with different ratios of graphene oxideto simulation antibiotics wastewater ciprofloxacin (CIP) was explored. The introduction of GO and ZnO enhances the visible light absorption of GO-ZnO/Ag3PO4, and makes GO-ZnO/Ag3PO4 have better separation efficiency of electron-hole pairs. When the mass fraction of GO is 1wt%, GO-ZnO/Ag3PO4 displays the best photocatalytic activity, and the degradation rate of CIP can reach 85.3% after 60 minutes of visible light. The capture experimentprove that, in the reaction process, superoxide radical (·O2) is the main active substance, and a heterojunction is formed between ZnO and Ag3PO4, which conforms to the Z-scheme electron transfer mechanism. The introduction of GO furtherly improves the rapid transfer of electrons and makes the Z-scheme system more stable. After six photocatalytic cycles, the degradation rate remained above 70%, indicating that the GO-ZnO/Ag3PO4 composite material has excellent stability.
  • 蜂窝夹层结构具有比模量大、隔音、隔热、吸能强、成本低等优点,在航空航天、交通运输、土木建筑、海洋船舶等许多领域都有广泛的应用[1]。碳纤维增强树脂复合材料(CFRP)蒙皮-铝蜂窝夹层板主要通过蜂窝芯和蒙皮的变形、损伤及内能形式将冲击能量加以耗散,从而达到吸能的目的[2-3]。CFRP板和铝蜂窝在生产和使用过程中都容易受到低速冲击的影响,而且蜂窝夹层板在低速冲击下的损伤一般是目视不可见的,但这种损伤却能够明显降低零部件的寿命和强度[4-5]。因此,研究结构参数对CFRP蒙皮-铝蜂窝夹层结构低速冲击性能的影响很有必要。

    国内外有大量关于蜂窝夹层板在不同载荷下力学性能的研究[6-11]。Zhang等[12]通过摆锤冲击试验和数值模拟方法研究了铝蜂窝夹层结构在低速冲击下的动力学特性,并得出结论:蜂窝芯是主要的吸能构件。Chen等[13]通过落锤式低速冲击试验与数值模拟方法验证了试验与仿真结果的一致性,并探究了CFRP面板-Nomex蜂窝夹层结构的损伤机制。A. Riccio等[14]结合落锤冲击试验和仿真模型探究了亚麻天然纤维蜂窝的吸能效果,试验与仿真结果吻合较好。Sun等[15]通过解析法研究了金属蒙皮蜂窝夹层板在低速冲击下的动态响应,通过与已有的试验结果对比,证明了其解析法的可靠性。Vincenzo Crupi等[16]结合试验方法和数值模型,研究了玻璃纤维增强树脂复合材料(GFRP)面板对低速冲击下铝蜂窝结构动力学性能的影响,发现GFRP面板是增强蜂窝夹层板能量吸收和承载能力的重要构件。Inés Ivañez等[17]基于材料用户子程序建立了CFRP面板-铝蜂窝夹层梁低速冲击有限元模型,通过多次试验对比验证了仿真模型的有效性,并得出结论:蜂窝夹层结构受低速冲击时,冲击能量较大时,蒙皮吸能较多,冲击能量较小时,蜂窝芯吸能较多。

    目前对不同材料蜂窝夹层板在低速冲击下动态响应的研究有很多[18-22],但CFRP蒙皮-铝蜂窝夹层板在低速冲击下的损伤模式相对较复杂,关于建立该类型夹层板在低速冲击下的精细化仿真模型,以探究其结构参数对抗低速冲击性能的影响以及各组件损伤对吸能占比的研究比较少,研究结构参数对该类型蜂窝夹层板低速冲击性能的影响,对其在实际工程中的应用及结构参数优化有重要的指导意义。本文使用半球头式落锤冲击试验平台和高速摄像分析平台,进行了蜂窝芯单元边长对CFRP蒙皮-铝蜂窝夹层板抗低速冲击性能影响的试验探究,根据试验结果验证了所建仿真模型的准确性。利用该数值模型进一步探究了蜂窝芯高度、蒙皮厚度和蜂窝芯壁厚等结构参数对蜂窝夹层板低速冲击性能的影响。

    基于D7766/D7766M—11标准[23],搭建了如图1所示的CFRP蒙皮-铝蜂窝夹层板落锤冲击试验平台,平台主要构成设备包括:XBL-300型落锤式低速冲击试验机及数据采集装置,厂家为长春科新试验仪器有限公司。其中,控制平台、落锤、夹具和防二次冲击装置是试验机的主要构件。使用的i-speed 2系列高速摄像机及配备的ProAnalyst数码分析软件由Xcitex公司提供,如图2所示。

    图  1  落锤式低速冲击试验平台
    Figure  1.  Low-speed impact test system of drop hammer
    图  2  高速摄像分析平台
    Figure  2.  High-speed camera analysis platform

    试件蒙皮均采用由威海光威复合材料有限公司提供的CFRP层合板,CFRP蒙皮是型号为T300/7901的碳纤维增强环氧树脂复合材料,铺层顺序为(45/-45/0)2s,单层厚度为0.1 mm,单块蒙皮长L=100 mm,宽W=100 mm,厚Tf =1.2 mm;铝蜂窝采用Al 3003-H19铝箔粘接而成,蜂窝芯壁厚Tc=0.06 mm,铝芯高Hc=20 mm,正六边形蜂窝芯单元边长Lc=2 mm、4 mm、6 mm;蜂窝芯与蒙皮之间采用LJM-170胶膜进行粘接;夹层板总体尺寸为100 mm×100 mm×22.4 mm。图3为蜂窝夹层板的几何构型示意图及试件,表1为T300/7901层合板的材料参数[24]表2为Al 3003-H19铝箔的材料参数。

    表  1  CFRP蒙皮的材料参数
    Table  1.  Mechanical properties of CFRP laminates
    T300/7901ValueAdhesiveValue
    E1/MPa125 000GCn/(Nmm1)0.52
    E2,E3/MPa11 300GCs,GCt/(Nmm1)0.92
    G12,G13/MPa5 430σn,max/MPa50
    G23/MPa3 979σs,max/MPa94
    ν12, ν230.3σt,max/MPa94
    ν230.42Kn/(Nmm3)100 000
    XT/MPa2 000Ks,Kt/(Nmm3)100 000
    XC/MPa1 100
    YT,ZT/MPa80
    YC,ZT/MPa280
    S/MPa120
    Notes: Ei(i=1,2,3) is Young’s modulus in i direction; Gij(i,j=1,2,3) is shear modulus in i-j plane; νij(i,j=1,2,3) is Poisson’s ratio in i-j plane; Xt/Xc and Yt/Yc are the tensile/compressive strengths in 1 and 2 directions, respectively; S is shear strength; GCn is toughness in tension; GCsand GCt are toughness components in shear; σn,max is maximum nominal stress of normal-only mode; σs,max and σt,max are maximum nominal stress in 1 and 2 directions, respectively; Kn is stiffness in tension; Ks and Kt are stiffness components in shear.
    下载: 导出CSV 
    | 显示表格
    表  2  Al 3003-H19铝箔材料参数
    Table  2.  Material properties of Al3003-H19 aluminum alloy foil
    PropertyValue
    Density/(kg·m−3)2 730
    Young’s modulus/GPa70
    Poisson’s ratio0.3
    Yield strength/MPa183
    下载: 导出CSV 
    | 显示表格
    图  3  碳纤维增强树脂复合材料(CFRP)蒙皮-铝蜂窝夹层板几何构型示意图及试件
    Figure  3.  Schematic of geometric configurations and specimens of aluminum honeycomb sandwich plates with carbon fiber reinforced polymer (CFRP) face sheets

    在进行落锤冲击试验时,用夹具将试件固定,设置好落锤下降高度后进行冲击试验。落锤完成冲击时,防二次冲击装置会立刻夹紧落锤。冲击时压力传感器采集的冲击力数据由数据采集装置记录并保存;同时通过高速摄像机记录冲击过程,以便使用ProAnalyst数码分析软件获得落锤在冲击过程中的运动数据。冲击过程中的冲击试验参数:落锤质量m=2.5 kg,半球形冲头直径为25 mm,落锤下降高度h=0.48 m,理论冲击能量为E=11.76 J。由于落锤在下降过程中存在摩擦,通过高速摄像平台测得落锤接触夹层板时初始冲击速度为3.0 m/s,即实际冲击能量为11.25 J。

    本文引用文献[24-25]中基于渐进损伤力学(CDM)方法对受损的CFRP蒙皮进行刚度退化,此方法定义了损伤因子Df,其值随着材料损伤的扩展而逐渐增大。层合板损伤后利用基于应力描述的三维Hashin准则进行损伤判定:

    纤维拉伸失效(σ110)

    (σ11XT)2+1S2(σ212+σ213)1 (1)

    纤维压缩失效(σ11<0)

    (σ11XC)21 (2)

    基体开裂失效(σ22+σ330)

    1Y2T(σ22+σ33)2+1S2(σ223σ22σ23)+1S2(σ212+σ213)1 (3)

    基体压溃失效(σ22+σ33<0)

    1YC[(YC2S)21](σ22+σ33)+14S2(σ22+σ33)2+1S2(σ223σ22σ23)+1S2(σ212+σ213)1 (4)

    其中,σijij=1,2,3)为CFRP面板单元的各个方向应力张量。

    基于内聚力(Cohesive)单元的双线性本构模型,建立了CFRP层合板胶层模型以模拟CFRP层合板的分层损伤。内聚力单元的双线性本构模型如图4所示[26-28]σ轴表示单元的应力,δ横轴表示单元的相对分离位移。当δ<δ0时,内聚力单元未破坏,其应力和相对位移呈线性关系,刚度为K,即O→A段;当δ0δ<δmax时,内聚力单元发生部分破坏,卸载时单元进入线性软化阶段,如图4中虚线部分,此时刚度为(1-Df)KDf为损伤因子,即O→A→B→O段,如重加载,初始阶段内聚力单元的σδ的关系即对应O→B段;当δδmax时,内聚力单元完全失效。

    图  4  内聚力单元的双线性本构模型
    Figure  4.  Bilinear constitutive model of cohesive element

    A点表示材料开始出现损伤,其对应的损伤准则为

    ((tn)2t0n)2+((ts)2t0s)2+((tt)2t0t)21 (5)

    其中,t0nt0st0t分别表示内聚力单元的法向和两个切向强度。AB段表示内聚力单元的损伤扩展,本文选择与试验吻合度较高的基于能量释放率的B-K准则[24]

    GCn+(GCsGCn)(GSGT)η=GC (6)

    其中:GS=Gs+GtGT=Gn+GSGCs=GCtGii=n,s,t)为Cohesive单元的应变能释放率;GCi为单元的临界应变能释放率;GC对应图4中△OAC的面积,即单元开裂对应的总临界能释放率;η为单元材料修正系数。

    基于CFRP层合板本构模型和用户材料子程序VUMAT,在ABAQUS有限元分析软件上建立蜂窝夹层板在低速冲击下的精细化仿真模型,如图5所示,蜂窝夹层板结构参数如表3所示。其中,层合板采用C3D8R单元,层间胶层采用COH3D8单元,铝蜂窝芯采用S4R壳单元;夹具和落锤均设置为刚体,夹具限制所有自由度,落锤仅保留冲击方向的自由度;假设蒙皮与蜂窝芯始终保持粘接,其接触类型设置为“Tie”,冲头与蒙皮采用“面-面接触”;为了节约计算成本,仅对临近冲击区域蒙皮进行网格细化,细化区域网格大小为1.5 mm×1.5 mm,其余区域网格大小为3 mm×3 mm,蜂窝芯网格大小为1 mm×2 mm。

    表  3  CFRP蒙皮-铝蜂窝夹层板的结构参数
    Table  3.  Structural parameters of aluminum honeycomb sandwich plate with CFRP face sheets
    LabelCell side length Lc/mmCore height Hc/mmFacesheet thickness Tf/mmCell wall thickness Tc/mm
    A12201.20.06
    A24201.20.06
    A36201.20.06
    B14101.20.06
    B24201.20.06
    B34301.20.06
    C14201.20.06
    C24201.80.06
    C34202.40.06
    D14201.20.06
    D24201.20.10
    D34201.20.14
    下载: 导出CSV 
    | 显示表格
    图  5  CFRP蒙皮-铝蜂窝夹层板的低速冲击有限元模型
    Figure  5.  Finite element model of aluminum honeycomb sandwich plate with CFRP face sheets for low-velocity impact simulation

    为了证明数值模拟方法所建有限元模型的准确性,以本文的试验参数为参照,将数值模拟计算结果与试验结果进行对比。在保证其他参数相同的条件下,蜂窝芯单元边长Lc=2 mm、4 mm、6 mm的CFRP蒙皮-铝蜂窝夹层板在质量m=2.5 kg、下降高度h=0.46 m的半球头落锤的冲击下(仿真中设置落锤初始速度为3 m/s),仿真与试验的接触力历程对比如图6所示,通过高速摄像平台采集分析了落锤的速度历程,仿真与试验速度历程对比如图7所示。

    图  6  试验与仿真中CFRP蒙皮-铝蜂窝夹层板的接触力历程对比
    Figure  6.  Comparison of experimental and numerical contact force historiesof aluminum honeycomb sandwich plate with CFRP face sheets
    图  7  试验与仿真中落锤的速度历程对比
    Figure  7.  Comparison of experimental and numerical velocity histories of the impactor

    通过对比图6图7的仿真和试验数据可知:在相同能量的冲击作用下,三种蜂窝芯单元边长夹层板在仿真中的接触力峰值分别为4 037 N、3 666 N和2 854 N,试 验d接触力峰值分别为3 799 N、3 476 N和2 811 N,仿真和试验接触力峰值的偏差分别为6.24%、5.47%和1.53%;仿真和试验的接触时长的差值分别为0.72 ms、0.40 ms和0.11 ms。试验与仿真在接触力历程和速度历程的总体趋势方面具有良好的一致性。

    将A组所有受冲击后的蜂窝夹层板由冲击区域的中心纵向切开,会发现受冲击位置的上蒙皮与芯层之间的胶层脱粘,蜂窝芯存在折叠和屈曲,上蒙皮的下表面均有部分基体开裂的现象。试验与仿真的蜂窝芯损伤深度对比如表4所示,不同蜂窝芯单元边长的夹层板在相同的冲击能量下得到了三种不同的变形深度,A组试验中受低速冲击区域蜂窝芯变形深度分别为2.15 mm、2.77 mm和4.32 mm,仿真中的蜂窝芯变形深度δ分别为2.20 mm、3.03 mm和4.10 mm。仿真与试验得到夹层板的蜂窝芯变形量之间的偏差分别为2.33%、9.39%和5.09%。由于本文设置的低速冲击能量较小,下蒙皮未发生任何形式的损伤,故不再在文中赘述其受载情况。

    表  4  试验与仿真中蜂窝芯损伤深度δ的对比
    Table  4.  Comparison of experimental and numerical deformations δ of honeycomb cores
    LabelTop face sheetCross-section
    ExperimentSimulation-Honeycomb core
    A1
    A2
    A3
    下载: 导出CSV 
    | 显示表格

    综上所述,所搭建的低速冲击有限元仿真模型可以较为准确地预测低速冲击下CFRP蒙皮-铝蜂窝夹层板的动力学响应。

    图8为三种不同蜂窝芯边长的CFRP蒙皮-铝蜂窝夹层板在质量m=2.5 kg、初始冲击速度为3 m/s的半球头落锤的冲击下,有限元模型预测的A组落锤动能历程,图9为预测的接触力-位移关系。可知,相同冲击能量下的蜂窝芯边长Lc分别为2 mm、4 mm、6 mm的CFRP蒙皮-铝蜂窝夹层板的最大变形深度依次增大,分别为5.26 mm、6.25 mm、7.40 mm。

    图  8  A组CFRP 蒙皮-铝蜂窝夹层板试件落锤的动能历程对比
    Figure  8.  Comparison of kinetic energy histories of the impactor for group A aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  9  A组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力-位移对比
    Figure  9.  Comparison of contact force-central displacement histories of the impactor for group A aluminum honeycomb sandwich plate with CFRP face sheets specimens

    通过分析可知:随着蜂窝芯单元边长的增大,夹层板受冲击时,落锤动能减小速率逐渐降低,接触时长逐渐增加,接触力峰值随之减小,夹层板受冲击位置的变形深度随之增大。可见,增大蜂窝芯单元的边长会降低蜂窝夹层板的刚度,但其吸能效果会随之增强。

    为了确定在低速冲击载荷下,蜂窝芯高度Hc对CFRP蒙皮-铝蜂窝夹层板吸能特性的影响,在仿真中使用了Hc=10 mm、20 mm、30 mm三种不同高度的蜂窝芯,蜂窝芯单元边长Lc=4 mm,蒙皮厚度Tf=1.2 mm,蜂窝芯壁厚Tc=0.06 mm,其余条件保持不变。图10为该工况下落锤的接触力历程对比,图11为落锤的动能历程对比,图12为落锤的接触力-位移关系对比。

    图  10  B组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力历程对比
    Figure  10.  Comparison of contact force histories of the impactor for group B aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  11  B组CFRP 蒙皮-铝蜂窝夹层板试件落锤的动能历程对比
    Figure  11.  Comparison of kinetic energy histories of the impactor for group B aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  12  B组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力-位移对比
    Figure  12.  Comparison of contact force-central displacement histories of the impactor for group B aluminum honeycomb sandwich plate with CFRP face sheets specimens

    图10~12可知:在蜂窝芯高度Hc=10 mm、20 mm、30 mm的该组仿真中,三种蜂窝夹层板在低速冲击载荷下,落锤的接触力峰值分别为3852N、3666N、3674N,接触时长分别为5.81 ms、5.85 ms、5.82 ms,最大变形深度分别为6.25 mm、6.26 mm、6.38 mm,且落锤的接触力历程、动能历程和接触力-位移的图形几乎保持一致。B组仿真中预测的蜂窝夹层板冲击损伤如表5所示。可知,蜂窝芯受冲击区域的最终变形量δ分别为2.97 mm、3.03 mm和3.08 mm,其变形量相差较小。由该组仿真结果可见,蜂窝芯高度的变化对于CFRP蒙皮-铝蜂窝夹层板的刚度和抗低速冲击性能影响不大。

    表  5  仿真预测的B组CFRP蒙皮-铝蜂窝夹层板冲击损伤
    Table  5.  Simulation predicted impact damage of group B aluminum honeycomb sandwich plate with CFRP face sheets
    LabelCross-section
    Honeycomb sandwich plateHoneycomb core
    B1
    B2
    B3
    下载: 导出CSV 
    | 显示表格

    为了确定蒙皮厚度Tf对低速冲击载荷下CFRP蒙皮-铝蜂窝夹层板吸能特性的影响,在仿真中使用了Tf=1.2 mm、1.8 mm、2.4 mm三种不同厚度的CFRP蒙皮,蜂窝芯单元边长为4 mm,蜂窝芯高度Hc=20 mm,蜂窝芯壁厚Tc=0.06 mm,其余条件保持不变。图13为该工况下落锤的接触力历程对比,图14为落锤的动能历程对比,图15为落锤的接触力-位移关系对比。

    图  13  C组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力历程对比
    Figure  13.  Comparison of contact force histories of the impactor for group C aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  14  C组CFRP 蒙皮-铝蜂窝夹层板试件落锤的动能历程对比
    Figure  14.  Comparison of kinetic energy histories of the impactor for group C aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  15  C组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力-位移对比
    Figure  15.  Comparison of contact force-central displacement histories of the impactor for group C aluminum honeycomb sandwich plate with CFRP face sheets specimens

    图13~15可知:在蒙皮厚度Tf=1.2 mm、1.8 mm、2.4 mm的该组仿真中,三种蜂窝夹层板在相同冲击能量的低速冲击载荷下,落锤的接触力峰值分别为3666N、3923N、4314N,接触时长分别为5.85 ms、5.13 ms、4.28 ms,最大变形深度分别为6.26 mm、5.14 mm、4.39 mm。C组仿真中预测的蜂窝夹层板冲击损伤如表6所示。可知,蜂窝芯受冲击区域的最终变形量δ分别为3.03 mm、2.41 mm和2.13 mm。随着蜂窝夹层板蒙皮厚度的增大,冲击时,落锤动能的减小速率随之增大,接触时间随之减少,接触力的峰值随之增大,夹层板受冲击区域的变形量随之减小。可见,蒙皮厚度的增加会使蜂窝夹层板的刚度增大,吸能效果随之降低。

    表  6  仿真预测的C组CFRP蒙皮-铝蜂窝夹层板冲击损伤
    Table  6.  Simulation predicted impact damage of group C aluminum honeycomb sandwich plate with CFRP face sheets
    LabelCross-section
    Honeycomb sandwich plateHoneycomb core
    C1
    C2
    C3
    下载: 导出CSV 
    | 显示表格

    为了探究低速冲击载荷下,蜂窝芯壁厚Tc对CFRP蒙皮-铝蜂窝夹层板吸能特性的影响,在仿真中使用了Tc=0.06 mm、0.10 mm、0.14 mm三种不同壁厚的蜂窝芯,蜂窝芯单元边长为4 mm,蜂窝芯高度Hc=20 mm,蒙皮厚度Tf=1.2 mm,其余条件保持不变。图16为该工况下落锤的接触力历程对比,图17为落锤的动能历程对比,图18为落锤的接触力-位移关系对比。

    图  16  DCFRP 蒙皮-铝蜂窝夹层板组试件落锤的接触力历程对比
    Figure  16.  Comparison of contact force histories of the impactor for group D aluminum honeycomb sandwich plate with CFRP face sheets specimens
    图  17  DCFRP 蒙皮-铝蜂窝夹层板组试件落锤的动能历程对比
    Figure  17.  Comparison of kinetic energy histories of the impactor for group D specimens
    图  18  D组CFRP 蒙皮-铝蜂窝夹层板试件落锤的接触力-位移对比
    Figure  18.  Comparison of contact force-central displacement histories of the impactor for group D aluminum honeycomb sandwich plate with CFRP face sheets specimens

    根据图16~18可知:在蜂窝芯壁厚Tc=0.06 mm、0.10 mm、0.14 mm的该组仿真中,三种蜂窝夹层板在相同冲击能量的低速冲击载荷下,落锤的接触力峰值分别为3666N、4153N、4454N,接触时长分别为5.85 ms、5.31 ms、4.99 ms,最大变形深度分别为6.26 mm、5.50 mm、5.28 mm。仿真预测的D组蜂窝夹层板冲击损伤如表7所示。可知,蜂窝芯受冲击区域的最终变形量δ分别为3.03 mm、2.83 mm和2.77 mm。随着蜂窝夹层板蜂窝芯壁厚的增大,在低速冲击下,落锤动能的减小速率随之增大,接触时间随之减少,落锤与夹层板之间的接触力峰值随之增大,夹层板受冲击区域的变形量随之减小。可见,增加蜂窝芯的壁厚会使蜂窝夹层板的刚度增大,抗低速冲击的性能增强。

    表  7  仿真预测的D组CFRP蒙皮-铝蜂窝夹层板冲击损伤
    Table  7.  Simulation predicted impact damage of group D aluminum honeycomb sandwich plate with CFRP face sheets
    LabelCross-section
    Honeycomb sandwich plateHoneycomb core
    D1
    D2
    D3
    下载: 导出CSV 
    | 显示表格

    表8为不同结构参数的CFRP蒙皮-铝蜂窝夹层板在相同能量的低速冲击下,各组件的吸能占比情况。可知:在本文设置的较低能量级冲击载荷下,CFRP蒙皮-铝蜂窝夹层板的吸能占比均大于60%,足以证明蜂窝夹层结构具有较好的冲击吸能特性;在该规格的冲击条件下,CFRP蒙皮-铝蜂窝夹层板最主要的吸能组件是铝蜂窝芯,上蒙皮吸能次之,下蒙皮吸能最少。由A组夹层板吸能占比分析可知,随着蜂窝芯单元边长的增大,蜂窝芯吸能占比逐渐增大,上蒙皮吸能占比逐渐减小,夹层板总吸能逐渐增大;由B组数据分析可知,随着蜂窝芯高度的增大,蜂窝芯吸能占比逐渐增大,上蒙皮吸能逐渐减少,夹层板总吸能逐渐增大;由C组数据分析可知,随着蒙皮厚度的增大,蜂窝芯层吸能占比逐渐减小,上蒙皮吸能占比逐渐增大,夹层板总吸能逐渐增大;由D组数据分析可知,随着蜂窝芯壁厚的增大,蜂窝芯吸能占比逐渐减小,上蒙皮吸能占比逐渐增大,夹层板总吸能逐渐增大。综上所述,在本文所设置的载荷条件下,增大蜂窝芯单元边长、蜂窝芯高度、蒙皮厚度和蜂窝芯壁厚,均能增加蜂窝夹层板的吸能量。然而吸能效果需结合碰撞时的接触时长、接触力峰值、变形损伤深度和吸能量综合考虑,故需结合图表才能得到合理的结论。

    表  8  不同结构参数的CFRP蒙皮-铝蜂窝夹层板组件吸能占比
    Table  8.  Absorbed energy rates by components of aluminum honeycomb sandwich plate with CFRP face sheets with different structural parameters %
    ParametersCell side length LcCore height HcFacesheet thickness TfCell wall thickness Tc
    A1A2A3B1B2B3C1C2C3D1D2D3
    Upper plate20.4317.2916.4919.5317.2916.0417.2926.9731.7217.2920.8830.02
    Honeycomb45.1650.0158.6038.4550.0157.3550.0143.2039.7850.0145.6141.75
    Lower plate1.881.702.512.151.701.701.701.080.721.702.693.32
    Impactor32.5331.0022.4039.8731.0024.9131.0028.0527.7831.0030.8224.91
    Sandwich plate67.3769.0077.6060.1369.0075.0969.0071.9572.2269.0069.1875.09
    下载: 导出CSV 
    | 显示表格

    建立了碳纤维增强树脂复合材料(CFRP)蒙皮-铝蜂窝夹层板精细化低速冲击仿真模型,通过对比不同蜂窝芯边长的夹层板在相同冲击能量下的仿真与试验结果,证明了试验与仿真结果具有较好的一致性。进而利用该数值模型探究了蜂窝芯高度、蒙皮厚度和蜂窝芯壁厚等结构参数对于蜂窝夹层板低速冲击性能的影响。

    (1)随着蜂窝芯单元边长的增大,夹层板受冲击时,落锤动能减小速率逐渐降低,接触时长逐渐增加,接触力峰值随之减小,夹层板受冲击位置的变形深度随之增大。可见,蜂窝芯单元边长尺寸的增大会降低蜂窝夹层板的刚度,但其吸能效果会随之增强。

    (2)蜂窝夹层板的芯层高度对夹层板的刚度及抗低速冲击性能影响较小。

    (3)增大蜂窝夹层板的蒙皮厚度,可以提高夹层板的刚度,但会降低夹层板的吸能效果。

    (4)增大蜂窝芯壁厚,会提高蜂窝夹层板的刚度和抗低速冲击性能。

    (5)在本文的低速冲击条件下,CFRP蒙皮-铝蜂窝夹层板的蜂窝芯是主要的吸能组件,上蒙皮吸能占比次之,下蒙皮吸能最少。

  • 图  1   纯ZnO、Ag3PO4、ZAP和GZAP-4的XRD图谱

    Figure  1.   XRD patterns of pure ZnO, Ag3PO4, ZAP and GZAP-4

    图  2   GZAP-4的XPS图谱:(a)全谱;(b) C 1s;(c) Ag 3d;(d) Zn 2p

    Figure  2.   XPS diagram of GZAP-4:(a) Full spectrum; (b) C 1s; (c) Ag 3d; (d) Zn 2p

    图  3   纯ZnO、Ag3PO4、ZAP和GZAP-4的FTIR图谱

    Figure  3.   FTIR images of pure ZnO, Ag3PO4, ZAP and GZAP-4

    图  4   样品的SEM图像

    Figure  4.   SEM image of the samples ((a) Pure ZnO; (b) Pure Ag3PO4; (c) ZAP; (d) GZAP-4)

    图  5   GZAP-4的EDS图谱

    Figure  5.   EDS diagram of GZAP-4

    图  6   Ag3PO4和GZAP-4的N2吸附-解吸等温线

    Figure  6.   N2 adsorption-desorption isotherm of Ag3PO4 and GZAP-4

    图  7   ZnO、Ag3PO4、ZAP和GZAP-4的UV-Vis DRS图(a)和Ag3PO4、ZAP和GZAP-4的PL光谱(b)

    Figure  7.   UV-Vis DRS diagram of ZnO, Ag3PO4, ZAP and GZAP-4 (a) as well as PL spectrum of Ag3PO4, ZAP and GZAP-4 (b)

    图  8   不同样品可见光降解CIP曲线(a)和对应样品准一级动力学拟合(b)

    Figure  8.   Visible light degradation curves of CIP by different samples (a) and quasi-first-order kinetic fitting of corresponding samples (b)

    图  9   GZAP-4循环6次光催化降解图

    Figure  9.   Photocatalytic degradation after 6 cycles of GZAP-4

    图  10   GZAP-4添加不同捕获剂对光催化的影响

    Figure  10.   The effect of adding different capture agents to GZAP-4 on photocatalysis

    图  11   可见光下Ag3PO4和GZAP-4的ESR DMPO-·O2光谱

    Figure  11.   ESR DMPO-·O2spectrum of Ag3PO4 and GZAP-4 under visible light

    图  12   ZnO和Ag3PO4的禁带宽度计算

    Figure  12.   Calculation of the band gap of ZnO and Ag3PO4

    图  13   GO-ZnO/Ag3PO4的光催化机制示意图

    Figure  13.   Schematic diagram of the photocatalytic mechanism of GO-ZnO/Ag3PO4

    表  1   复合材料命名

    Table  1   Composite name

    Composite nameMass ratio of GO to Ag3PO4/%Lable
    ZnO/Ag3PO4 0 ZAP
    1GO-Ag3PO4 1 GAP
    0.1GO-ZnO/Ag3PO4 0.1 GZAP-1
    0.2GO-ZnO/Ag3PO4 0.2 GZAP-2
    0.5GO-ZnO/Ag3PO4 0.5 GZAP-3
    1GO-ZnO/Ag3PO4 1 GZAP-4
    2GO-ZnO/Ag3PO4 2 GZAP-5
    下载: 导出CSV

    表  2   Ag3PO4和GZAP-4的比表面积、孔径及孔体积数据

    Table  2   Specific surface area, pore size and pore volume data of Ag3PO4 and GZAP-4

    SampleSurface area/
    (m2·g−1)
    Average pore sizes/nmPore volume/(cm3·g−1)
    Ag3PO4 9.59 8.51 0.0077
    GZAP-4 16.47 6.23 0.0751
    下载: 导出CSV
  • [1]

    SHI H, YANG S, HAN C, et al. Fabrication of Ag/Ag3PO4/WO3 ternary nanoparticles as superior photocatalyst for phenol degradation under visible light irradiation[J]. Solid State Sciences,2019,96:105967.

    [2]

    LIANG C, FENG H, NIU H, et al. A dual transfer strategy for boosting reactive oxygen species generation in ultrathin Z-scheme heterojunction driven by electronic field[J]. Chemical Engineering Journal,2020,384:123236.

    [3]

    GANGULY P, BYRNE C, BREEN A, et al. Antimicrobial activity of photocatalysts: Fundamentals, mechanisms, kinetics and recent advances[J]. Applied Catalysis B: Environmental,2018,225:51-75.

    [4]

    MU C, ZHANG Y, CUI W, et al. Removal of bisphenol A over a separation free 3D Ag3PO4 -graphene hydrogel via an adsorption-photocatalysis synergy[J]. Applied Catalysis B: Environmental,2017,212:41-49.

    [5] 宋萃, 戚明颖, 刘金芳, 等. Ag3PO4/羟基磷灰石复合光催化剂的制备及对亚甲基蓝的高效降解[J]. 复合材料学报, 2020, 37(6):1418-1425.

    SONG Cui, QI Mingying, LIU Jinfang, et al. Preparation of Ag3PO4/HAP composite photocatalyst and its efficient degradation of methylene blue[J]. Acta Materiae Compositae Sinica,2020,37(6):1418-1425(in Chinese).

    [6]

    Al K M, GUPTA S S, CHAKRABORTTY D. Ag3PO4-based nanocomposites and their applications in photodegradation of toxic organic dye contaminated wastewater: Review on material design to performance enhancement[J]. Journal of Saudi Chemical Society,2020,24(1):20-41.

    [7]

    MU Z, HUA J, KUMAR T S, et al. Visible light photocatalytic activity of Cu, N co-doped carbon dots/Ag3PO4 nanocomposites for neutral red under green LED radiation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2019,578:123643.

    [8]

    LI Q, WANG F, HUA Y, et al. Deposition-precipitation preparation of Ag/Ag3PO4/WO3 nanocomposites for efficient Visible-light degradation of rhodamine B under strongly acidic/alkaline conditions[J]. Journal of Colloid and Interface Science,2017,506:207-216.

    [9]

    AMORNPITOKSUK P, SUWANBOON S. Photocatalytic decolorization of methylene blue dye by Ag3PO4–AgX (X=Cl, Br and I) under visible light[J]. Advanced Powder Technology,2014,25(3):1026-1030.

    [10]

    YI Z, LI X, WU H, et al. Fabrication of ZnO@Ag3PO4 core-shell nanocomposite arrays as photoanodes and their photoelectric properties[J]. Nanomaterials (Basel),2019,9(9):1254-1265.

    [11]

    LIU J, XIE F, LI R, et al. TiO2-x/Ag3PO4 photocatalyst: Oxygen vacancy dependent visible light photocatalytic performance and BPA degradative pathway[J]. Materials Science in Semiconductor Processing,2019,97:1-10.

    [12]

    RAO X, DOU H, LONG D, et al. Ag3PO4/g-C3N4 nanocomposites for photocatalytic degradating gas phase formaldehyde at continuous flow under 420 nm LED irradiation[J]. Chemosphere,2020,244:125462.

    [13]

    YOU L, GAO M, LI T, et al. Investigation of the kinetics and mechanism of Z-scheme Ag3PO4/WO3 p-n junction photocatalysts with enhanced removal efficiency for RhB[J]. New Journal of Chemistry,2019,43(43):17104-17115.

    [14]

    SHAO B, LIU X, LIU Z, et al. A novel double Z-scheme photocatalyst Ag3PO4/Bi2S3/Bi2O3 with enhanced visible-light photocatalytic performance for antibiotic degradation[J]. Chemical Engineering Journal,2019,368:730-745.

    [15]

    LI Z, DAI K, ZHANG J, et al. Facile synthesis of novel octahedral Cu2O/Ag3PO4 composite with enhanced visible light photocatalysis[J]. Materials Letters,2017,206:48-51.

    [16]

    LV J, ZHU Q, ZENG Z, et al. Enhanced photocurrent and photocatalytic properties of porous ZnO thin film by Ag nanoparticles[J]. Journal of Physics and Chemistry of Solids,2017,111:104-109.

    [17]

    VAIANO V, MATARANGOLO M, MURCIA J J, et al. Enhanced photocatalytic removal of phenol from aqueous solutions using ZnO modified with Ag[J]. Applied Catalysis B: Environmental,2018,225:197-206.

    [18]

    JIN C, LIU G, ZU L, et al. Preparation of Ag@Ag3PO4@ZnO ternary heterostructures for photocatalytic studies[J]. Journal of Colloid and Interface Science,2015,453:36-41.

    [19]

    ZHONG J, LI J, WANG T, et al. Improved solar-driven photocatalytic performance of Ag3PO4/ZnO composites benefiting from enhanced charge separation with a typical Z-scheme mechanism[J]. Applied Physics A,2016,122:4.

    [20]

    MARTÍN-GÓMEZ A N, NAVÍO J A, JARAMILLO-PÁEZ C, et al. Hybrid ZnO/Ag3PO4 photocatalysts, with low and high phosphate molar percentages[J]. Journal of Photochemistry and Photobiology A: Chemistry,2020,388:112196.

    [21]

    DONG C, WU K, LI M, et al. Synthesis of Ag3PO4-ZnO nanorod composites with high visible-light photocatalytic activity[J]. Catalysis Communications,2014,46:32-35.

    [22]

    LI Y, CUI W, LIU L, et al. Removal of Cr(VI) by 3D TiO2-graphene hydrogel via adsorption enriched with photocatalytic reduction[J]. Applied Catalysis B: Environmental,2016,199:412-423.

    [23] 张转芳, 唐林, 孙立, 等. CuS/GO纳米复合材料的制备及光催化降解性能[J]. 精细化工, 2019, 36(02):237-242.

    ZHANG ZhuanFang, TANG Lin, SUN Li, et al. Preparation of CuS/GO Nanocomposite and Its Photocatalytic Degradation Activity[J]. Fine Chemicals,2019,36(02):237-242(in Chinese).

    [24] 杨程, 时双强, 郝思嘉, 等. 石墨烯光催化材料及其在环境净化领域的研究进展[J]. 材料工程, 2020(7):1-13.

    YANG Cheng, SHI Shuangqiang, HAO Sijia, et al. Research progress in graphene based photocatalytic materials and applications in environmental purification[J]. Journal of Materials Engineering,2020(7):1-13(in Chinese).

    [25]

    CHEN F, YANG Q, LI X, et al. Hierarchical assembly of graphene-bridged Ag3PO4/Ag/BiVO4 (40) Z-scheme photocatalyst: An efficient, sustainable and heterogeneous catalyst with enhanced visible-light photoactivity towards tetracycline degradation under visible light irradiation[J]. Applied Catalysis B: Environmental,2017,200:330-342.

    [26]

    YAN J, WANG C, XU H, et al. AgI/Ag3PO4 heterojunction composites with enhanced photocatalytic activity under visible light irradiation[J]. Applied Surface Science,2013,287:178-186.

    [27]

    THI V H, LEE B. Effective photocatalytic degradation of paracetamol using La-doped ZnO photocatalyst under visible light irradiation[J]. Materials Research Bulletin,2017,96:171-182.

    [28]

    LI Y, XIAO X, YE Z. Fabrication of BiVO4/RGO/Ag3PO4 ternary composite photocatalysts with enhanced photocatalytic performance[J]. Applied Surface Science,2019,467-468:902-911.

    [29]

    LIANG C, ZHANG L, GUO H, et al. Photo-removal of 2, 2′4, 4′-tetrabromodiphenyl ether in liquid medium by reduced graphene oxide bridged artificial Z-scheme system of Ag@Ag3PO4/g-C3N4[J]. Chemical Engineering Journal,2019,361:373-386.

    [30] 张志伟, 徐斌, 张毅敏, 等. GO/(CeO2-TiO2)改性复合膜紫外光催化去除氨氮、DOC[J]. 中国环境科学, 2020, 40(3):1116-1122. DOI: 10.3969/j.issn.1000-6923.2020.03.022

    ZHANG Zhiwei, XU Bin, ZHANG Yimin, et al. Ultraviolet photocatalytic removal of ammonia nitrogen and DOC by GO/(CeO2-TiO2) modified composite membrane[J]. Chinese Environmental Science,2020,40(3):1116-1122(in Chinese). DOI: 10.3969/j.issn.1000-6923.2020.03.022

    [31]

    WANG H, ZOU L, SHAN Y, et al. Ternary GO/Ag3PO4/AgBr composite as an efficient visible-light-driven photocatalyst[J]. Materials Research Bulletin,2018,97:189-194.

    [32]

    CHEN X, DAI Y, WANG X, et al. Synthesis and characterization of Ag3PO4 immobilized with graphene oxide (GO) for enhanced photocatalytic activity and stability over 2, 4-dichlorophenol under visible light irradiation[J]. Journal of Hazardous Materials,2015,292:9-18.

    [33] 常亮亮, 于艳, 曹宝月, 等. 可循环利用BiOBr/石墨烯水凝胶复合材料的制备及其对丁基钠黄药的降解性能[J]. 复合材料学报, 2020, 36(1):1-10.

    CHANG Liangliang, YU Yan, CAO Baoyue, et al. Preparation of Recyclable BiOBr/Graphene Hydrogel Composite and Its Photodegradation of Sodium Butyl Xanthate[J]. Acta Materiae Compositae Sinica,2020,36(1):1-10(in Chinese).

    [34] 胡金娟, 马春雨, 王佳琳, 等. Ag-Ag2O/TiO2-g-C3N4纳米复合材料的制备及可见光催化性能[J]. 复合材料学报, 2020, 37(6):1401-1410.

    HU Jinjuan, MA Chunyu, WANG Jialin, et al. Preparation and photocatalytic properties of Ag-Ag2O/TiO2-g-C3N4 nanocomposites[J]. Acta Materiae Compositae Sinica,2020,37(6):1401-1410(in Chinese).

  • 期刊类型引用(0)

    其他类型引用(4)

图(13)  /  表(2)
计量
  • 文章访问数:  1902
  • HTML全文浏览量:  467
  • PDF下载量:  90
  • 被引次数: 4
出版历程
  • 收稿日期:  2020-07-15
  • 录用日期:  2020-08-26
  • 网络出版日期:  2020-09-09
  • 刊出日期:  2021-07-14

目录

/

返回文章
返回