Silica-Based Nanocoating Doped by Layered Double Hydroxides to Enhance the Paperboard Barrier Properties

Paperboard is an environment-friendly multi-layer material widely used for packaging applications. However, for food packaging paperboard lacks essential barrier properties towards oxygen and water vapor. Conventional solutions to enhance these barrier properties (e.g. paperboard film coating with synthetic polymers) require special manufacturing facilities and difficult the end-of-life disposal and recycling of the paperboard. Paperboard coating with silica-based formulations is an eco-friendly alternative hereby disclosed. Silica-nanocoatings were prepared by sol-gel synthesis, with or without the addition of Zn(2)-Al-NO3 layered double hydroxides (LDHs), and applied on the surface (ca 2 g/m2) of industrial paperboard samples by a roll-to-roll technique. The physicochemical features of silica-nanocoatings were studied by FTIR-ATR, SEM/EDS, XRD analysis and surface energy measurements. The barrier properties of uncoated and silica-coated paperboard were accessed by water vapor transmission rate (WVTR) and oxygen permeability (Jo2) measurements. The best barrier results were obtained for paperboard coated with a mixture of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES), with and without the incorporation of LDHs.

Synthesis of LDHs and Rheological Properties of Laponite/LDHs Dispersions

The chemical composition, morphology of the particles of positively charged layered doubl?hydroxides (LDHs) were studied by ICP, Mastersizer, TEM. The preliminary results indicated that with adding LDHs to 1% laponite dispersion the yield stress of laponite/LDHs mixed dispersions increased at first, then decreased dramatically to a minimum, and the yield stress rose again when LDHs increased further.

Multifunctional Polypyrrole-silver Coated Layered Double Hydroxides Embedded into a Biodegradable Polymer Matrix for Enhanced Antibacterial and Gas Barrier Properties

In this study,polypyrrole-silver coated layered double hydroxides(LDHs@PPy-Ag)was prepared by chemical polymerization of pyrrole(Py)with silver ions.Silver nanoparticles(AgNPs)could be uniformly reduced onto PPy coatings in situ by redox reaction during simultaneous polymerization process.And LDHs@PPy-Ag/poly(ε-caprolactone)(PCL)nanocomposites were fabricated by solution casting method.It is revealed that spherical AgNPs are loaded on PPy coatings uniformly.Particularly,compared with pure PCL,LDHs@PPy-Ag/PCL nanocomposites with incorporation of only 1 wt%LDHs@PPy-Ag show a 17%increase in tensile strength(36.5 MPa)and a 29%increase in elongation at break(822%).Upon PPy-Ag coatings onto original LDHs,oxygen relative permeability of LDHs@PPy-Ag/PCL nanocomposites decreases to 52%with the same addition.Meanwhile,due to the double antibacterial activity of PPy and AgNPs,the antibacterial rate of LDHs@PPy-Ag reaches 100%.And the corresponding LDHs@PPy-Ag/PCL nanocomposites also show outstanding antibacterial activity.Considering the superiority of their comprehensive performance,antibacterial LDHs@PPy-Ag/PCL nanocomposites can be used further for the application as biodegradable polymeric active packaging materials.

Controllable magnetic properties of cobalt ferrite particles derived from layered double hydroxide precursors

Cobalt ferrite CoxNi1-xFe2O4 （x = 0, 0.5, 1 ） particles with controllable magnetic properties have been prepared by calcination of co-substituted NiFe^2＋Fe^3＋ -layered double hydroxide （NiFe^2＋Fe^3＋-LDH） precursors prepared via a scalable method involving separate nucleation and aging steps （SNAS）. Their structural and magnetic characteristics were investigated by powder X-ray diffraction （XRD）, scanning electron microscopy （SEM） and vibrating sample magnetometry （VSM）. Measurements of magnetic properties show that the saturation magnetization （Ms） and coercivity （He） of the calcined products increased with increasing cobalt content. The LDH precursor-based product obtained by calcination of a mixture of CoFe^2＋Fe3^＋-LDH and NiFe^2＋Fe^3＋ -LDH powders with a Co/Ni molar ratio of 1：1, exhibits a moderate value of Ms and an increased value of He compared to the corresponding values for an Ni0.5Co0.5Fe2O4 material prepared by calcination of a Co0.5Ni0.5Fe^2＋Fe^3＋-LDH precursor, and a physical mixture of CoFe2O4 and NiFe2O4 with a Co/Ni molar ratio of 1 ： 1. These results may provide a way to regulate magnetic anisotropy of ferrite spinels by varying the composition of the LDH precursors.

Enhanced protective coatings on Ti-10V-2Fe-3Al alloy through anodizing and post-sealing with layered double hydroxides

Anodic oxidation is a prevalent technique to introduce superior corrosion and wear resistance upon the surface of titanium(Ti)alloys,in which the selection of appropriate electrolytes and defect-sealing strategies is a key.This study aims to address such issues through anodizing Ti-10V-2Fe-3Al alloy in malic acid,followed by a post-sealing treatment with Mg-Al layered double hydroxides(LDHs).The characteristics of the samples were investigated using scanning electron microscopy(SEM),atomic force microscopy(AFM),glow discharge optical emission spectroscopy(GDOES),X-ray diffraction(XRD)and energy-dispersive X-ray spectroscopy(EDS).SEM micrographs reveals that the anodic coating had a surface full of bulges and cracks,and was almost sealed by the following LDHs treatment.XRD pattern indicate that the anodic coating was mainly consisted of amorphous TiO2 with a small fraction of anatase,but its crystallization degree was increased through the post-sealing.Moreover,electrochemical and tribological measurements demonstrate that corrosion current density was 2.8×10-6,2.0×10-7,5.9×10-9A cm-2,and wear rate was 1.45×10-3,1.30×10-4 and 6.90×10-5 mm3 N-1 m-1 for respective bare Ti-10V-2Fe-3Al alloy substrate,anodized specimens without and with the LDHs post treatment.Finally,a plausible wear mechanism was proposed.

SYNERGISTIC EFFECTS OF LAYERED DOUBLE HYDROXIDE WITH PHOSPHORUS-NITROGEN INTUMESCENT FLAME RETARDANT IN PP/EPDM/IFR/LDH NANOCOMPOSITES

Synergistic effects of layered double hydroxide （LDH） with intumescent flame retardanct （IFR） of phosphorusnitrogen （NP） compound in the polypropylene/ethylene-propylene-diene/IFR/LDH （PP/EPDM/IFR/LDH） nanocomposites and related properties were studied by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, limiting oxygen index （LOI）, UL-94 test, cone calorimeter test （CCT） and thermo-gravimetric analysis （TGA）. The XRD and TEM results show that the intercalated and/or exfoliated nanocomposites can be obtained by direct melt-intercalation of PP/EPDM into modified LDH and that LDH can promote the IFR additive NP to disperse more homogeneously in the polymer matrix. The SEM results provide positive evidence that more compact charred layers can be obtained from the PP/EPDM/NP/LDH sample than those from the PP/EPDM/LDH and PP/EPDM/NP samples during burning. The LOI and UL-94 rating tests show that the synergetic effects of LDH with NP can effectively increase the flame retardant properties of the PP/EPDM/NP/LDH samples. The data from the CCT and TGA tests indicate that the PP/EPDM/NP/LDH samples apparently decrease the HRR and MLR values and thus enhance the flame retardant properties and have better thermal stability than the PP/EPDM/LDH and PP/EPDM/NP samples.

Supermolecular layered double hydroxides

Research progresses in the layered double hydroxides [M2+(1-x)M3+x(OH)2]x+An-x/n.mH2O intercalatedwith metal coordinate ions or oxometalates in the last ten years are reviewed. These layered double hydroxides are mainly intercalated with polyoxometalate (POM) ions, a LiAl-LDH photochemical assembly containing TiO2 and CH3(CH2)12COO- anions, together with Zn(TPPC) (porphy-rin derivate) and macrocyclic ligand-containing porphyrin derivate anions. Emphasis is put on the synthesis methods for intercalation of the anions into the interlayer regions, the characterization techniques and structures for the layeredcompounds and the newest research progress in the fields such as catalysis. The review also forecasts the prospects of the field.

Synergistic Effect of Carbon Nanotubes and Layered Double Hydroxides on the Mechanical Reinforcement of Nylon-6 Nanocomposites

Synergistic effect in network formation of nylon-6 （PA6） nanocomposites containing one dimensional （ID） multi-walled carbon nanotubes （CNTs） and two dimensional （2D） layered double hydroxide （LDH） platelets on improving the mechanical properties has been studied. Mechanical tests show that, with incorporation of 1 wt% LDHs and 0.5 wt% CNTs, the tensile modulus, the yield strength as well as the hardness of the ternary composite are greatly improved by about 230%, 128% and 110% respectively, as compared with neat PA6. This is mainly attributed to the unique, strong interactions between the CNTs and the LDHs as well as the jammed network-like structure thus formed between the nanofillers, as confirmed by the morphological observations. As compared with the binary nanocomposites, a much enhanced solid-like behavior in the terminal region of the rheological curves can clearly be observed for the ternary system, which also indicates the formation of a percolating filler network.

Tribological behavior of layered double hydroxides with various chemical compositions and morphologies as grease additives

The layered double hydroxide(LDH)is a kind of natural mineral,which can also be manually prepared.It has been practically applied in various fields due to its unique crystal structure and diversity of composition,size,and morphology.In this work,LDHs with different chemical compositions(Co^(2+),Mg^(2+),Zn^(2+),and Ni^(2+))and topographical features(flower‐like,spherical,and plate‐like)were successfully prepared by controlling the reaction conditions.Then,they were mechanically dispersed into base grease and their tribological properties were evaluated by a ball‐on‐disk tester under a contact pressure of 2.47 GPa.It was found that the variation of morphology,instead of chemical composition,had great influence on the tribological performance.The“flower‐like”LDH sample with high specific surface area(139 m^(2)/g)was demonstrated to show the best performance.With 1 wt%additive,the wear volume was only about 0.2%of that lubricated by base grease.The tribofilm with unique microscopic structure and uniform composition was derived from tribochemical reaction between LDH additives and sliding solid surfaces,effectively improving tribological properties of the lubrication system.This work provided the guidance for optimizing lubricant additives and held great potential in future applications.

Effect of modified MgAl-LDH coating on corrosion resistance and friction properties of aluminum alloy

The in-situ growing approach was utilized in this article to construct the magnesium–aluminum layered double hydroxide(MgAl-LDH)film on the surface of a 1060 aluminum anodized film.To improve the corrosion resistance and friction qualities of aluminum alloy,the MgAl-LDH coating was treated using stearic acid(SA)and thiourea(TU).The aluminum substrate and anodized aluminum film layer corroded to varying degrees after 24 h of immersion in 3.5%(mass)NaCl solution,while the modified hydrotalcite film layer continued to exhibit the same microscopic morphology even after being immersed for 7 d.The results show that the synergistic action of thiourea and stearic acid can effectively improve the corrosion resistance of the MgAl-LDH substrate.The tribological testing reveals that the hydrotalcite film layer and the modified film layer lowered the friction coefficient of the anodized aluminum surface substantially.The results of the simulations and experiments demonstrate that SA forms the dense LDH-TU interlayer film layer by exchanging NO_(3)^(-)ions between TU layers on the one hand and the LDH-SA film layer by adsorption on the surface of LDH on the other.Together,these two processes create LDH-TUSA,which can significantly increase the substrate’s corrosion resistance.This synergistically modified superhydrophobic and retardant hydrotalcite film layer offers a novel approach to the investigation of wear reduction and corrosion protection on the surface of aluminum and its alloys.

层状双羟基氢氧化物及其衍生物在锂硫电池中的应用

锂硫电池具有超高的理论能量密度、较低的材料成本,是极有前途的下一代储能体系。但硫导电性差、充放电过程中的穿梭效应、体积膨胀、负极锂枝晶等问题造成锂硫电池的比容量低、容量衰减严重、库仑效率差,影响了其实际应用。层状双羟基氢氧化物(LDHs)是一种二维材料,具有可调节的插层结构、可控的表面化学性质和独特的拓扑转换特性,作为储能材料受到了广泛的关注。LDHs对多硫化物具有良好的约束能力,作为锂硫电池正极硫载体可以高效吸附和催化充放电过程中产生的多硫化物,减少多硫化物的迁移,加快氧化还原反应动力学,从而提升锂硫电池的电化学性能。此外,二维LDHs可涂覆于隔膜作为正极与隔膜间的中间层,通过物理作用阻挡多硫化物向负极的迁移,抑制穿梭效应;LDHs用于锂负极可以促进金属锂的均匀成核和沉积。目前LDHs在锂硫电池中应用广泛,本文综述了LDH及其衍生物在锂硫电池中的应用优势,介绍了其在锂硫电池正极、中间层、负极中的应用现状,指出了LDHs材料在锂硫电池中的发展方向。

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe-Layered Double Hydroxide-Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes （CNTs） and flame retardancy of layered double hydroxide （LDH） in epoxy resin （EP）, organic nickel-iron layered double hydroxide （ONiFe-LDH-CNTs） hybrids were assembled through co-precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe-LDH-CNTs nano- composites containing 4 wt% of ONiFe-LDH-CNTs with different ratios of ONiFe-LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy （TEM）. The results revealed a coexistence of exfoliated and intercalated ONiFe-LDH- CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe-LDH-CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe-LDH and synergistic effect between ONiFe-LDH and CNTs.

Biodegradable Poly(propylene carbonate)/Layered Double Hydroxide Composite Films with Enhanced Gas Barrier and Mechanical Properties

Relatively well crystallized and high aspect ratio Mg-Al layered double hydroxides（LDHs） were prepared by coprecipitation process in aqueous solution and further rehydrated to an organic modified LDH（OLDH） in the presence of surfactant. The intercalated structure and high aspect ratio of OLDH were verified by X-ray diffraction（XRD） and scanning electron microscopy（SEM）. A series of poly（propylene carbonate）（PPC）/OLDH composite films with different contents of OLDH were prepared via a melt-blending method. Their cross section morphologies, gas barrier properties and tensile strength were investigated as a function of OLDH contents. SEM results show that OLDH platelets are well dispersed within the composites and oriented parallel to the composite sheet plane. The gas barrier properties and tensile strength are obviously enhanced upon the incorporation of OLDH. Particularly, PPC/2%OLDH film exhibits the best barrier properties among all the composite films. Compared with pure PPC, the oxygen permeability coefficient（OP） and water vapor permeability coefficient（WVP） is reduced by 54% and 17% respectively with 2% OLDH addition. Furthermore, the tensile strength of PPC/2%OLDH is 83% higher than that of pure PPC with only small lose of elongation at break. Therefore, PPC/OLDH composite films show great potential application in packaging materials due to its biodegradable properties, superior oxygen and moisture barrier characteristics.

层状双金属氢氧化物(LDHs)对SBS改性沥青抗老化性能的影响研究

为了增强SBS改性沥青(SMB)的抗老化性能,利用层状双金属氢氧化物(LDHs)的独特结构对SMB进行改性。研究了LDHs对SMB的物理性能、高低温流变性能和化学结构的影响规律。研究结果表明:LDHs的加入有助于提高SMB的弹性性能,提升SMB的高温稳定性能;老化后,沥青分子发生氧化反应导致SMB中含氧官能团(S=O和C=O)含量增加,同时SBS分子链发生断裂引起SMB中碳碳双键官能团(C=C)含量减少,这些变化使SMB的物理性能、高温抗车辙性能和低温抗疲劳开裂性能发生劣化,导致其变硬变脆;LDHs的加入可以阻止沥青分子的氧化反应和SBS分子链断裂,减缓沥青分子的老化和SBS老化降解,减轻老化对SMB物理性能和高低温流变性能的破坏,增强SMB的抗老化能力,为建设长寿命的SMB路面提供技术支持。

Crystallization Behavior and Thermal Properties of PP/MgAl LDH Nanocomposites Prepared in Non-polar Solution

Polypropylene（PP）/MgAl layered double hydroxide（MgAl LDH） nanocomposites were synthesized by refluxing PP and dodecyl sulfate-intercalated MgAI LDH[MgAI（DS）] in non-polar xylene. Their structure, thermal and crystallization properties were studied via X-ray diffraction（XRD）, transmission electron microscopy（TEM）, thermogravimetric analysis（TGA）, differential scanning calorimetry（DSC）, and polarized light microscopy（PLM）. The nanoscaled dispersion of MgAI（DS） nanolayeres in the PP matrix was verified by the disappearance of the d（003） XRD diffraction peak of MgAI（DS） and observation of TEM image. The DSC data show that the SDS/LDH inorganic components negatively affect the crystallization properties of PP and decrease the size of PP sphcrulites because the inorganic components act as additional nuclei. The PP/MgA1 LDH nanocomposites have a faster charring progress in a temperature range of 250--430 ℃ and a better thermal stability above 320℃ than pure PP.

环境友好脂肪酸型离子液体的流变学与摩擦学性能

为研究不同结构脂肪酸离子液体的流变学及其对润滑油性能的影响,以蓖麻油酸、油酸、二聚酸及胆碱为原料,制备3种环境友好型润滑材料([cho][ricinoleat],[cho][oleat],[cho][dimer]),采用流变仪和SRV摩擦试验机研究其流变学和摩擦学性能,采用扫描电子显微镜(SEM)和X-射线能谱仪(EDS)对磨损表面进行分析,初步探讨其润滑机制。结果表明:制备的[cho][ricinoleate]和[cho][dimer]是离子液体,室温下以液体状态存在,而[cho][oleic acid]室温下是以半固体的形态存在,类似润滑脂;随着温度和剪切速率的变化,[cho][ricinoleate]和[cho][dimer]黏度始终大于150BS基础油,其中[cho][dimer]黏度最大,并具有最优的减摩和抗磨性能,其主要原因可以推测为离子液体在金属表面形成双电层结构的吸附膜,以及离子液体较高的黏度增加了油膜厚度以及承载能力。

层状双金属氢氧化物对高黏沥青耐久性能影响研究

为了提升高黏沥青的耐久性,采用层状双金属氢氧化物(LDHs)对其进行改性,并研究了LDHs对高黏沥青老化前后的物理性能、温度敏感性以及低温流变性能的影响。研究结果表明,老化导致高黏沥青性能显著劣化,黏弹性发生破坏,弹性行为明显增加,黏性行为显著减弱;相比于未改性高黏沥青,LDHs的掺入明显抑制了老化对高黏沥青物理性能、温度敏感性、低温流变性能的破坏,增强了高黏沥青的耐久性,使其在老化过程中能够保持较好的物理流变性能。

Mg-Fe-MMH-钠质蒙脱土分散体系的触变性研究

触变性是分散体系一种复杂的流变学性质,指流变性质随剪切时间而发生变化的现象.以往研究过程中,先后发现了切稀现象和切稠现象,即正触变性和负触变性.最近,我们又发现了复合触变性,即一个体系可先后呈现正触变性和负触变性特征.研究了Mg-Fe型混合金属氢氧化物(简称MMH)-钠质蒙脱土(简称MT)分散体系的触变性,发现在不同MMH/MT质量比条件下,可分别呈现正触变性、负触变性,另外又观察到了复合触变性.在所研究的MMH/MT质量比范围(0～0.5)内,随MMH/MT质量比增大,体系的触变性发生负触变性-正触变性-复合触变性-负触变性的转化.考察了电解质NaCl对触变性的影响,发现不改变触变性的类型.探讨了各种触变性产生的原因,提出了“分散粒子-空间连续网络结构-密实聚集体”机理,较合理地解释了观察到的复合触变现象.

水滑石的合成、改性及其在功能复合材料中的应用

介绍了水滑石的结构和性能,分析了其典型的层状结构及其离子可交换性;着重介绍了水滑石的合成方法,如共沉淀法、离子交换法和焙烧还原法等,并对比了各种方法的特点;水滑石的改性主要是进行有机化改性,改性之后的水滑石才能与聚合物之间产生良好的结合力;重点综述了水滑石与高分子材料复合以后制备的功能材料或纳米复合材料的研究进展,以期为水滑石的进一步研究提供帮助。

LDHs材料的结构、性质及其应用研究进展

LDHs(layered double hydroxides)是一类具有双金属氢氧化物层结构的新型无机材料,其酸碱性、热稳定性、层间阴离子可交换性以及结构记忆效应等特性在诸多领域中得到了广泛应用,成为当前研究的热点。针对国内外研究现状,本文综述了LDHs材料的基本性质、层间不同种阴离子及插层阴离子的化学作用。在此基础上,概括了LDHs材料的制备、表征方法和相关领域的应用,介绍了其在不同溶剂中进行剥离的研究进展,指出能否将其工业化扩大生产是制约其应用的重要因素,同时也分析了当前需要解决的相关问题,为今后LDHs材料的研究提供借鉴。