Characterization and Selection of Microcrystalline Cellulose from Oil Palm Empty Fruit Bunches for Strengthening Hydrogel Films

Microcrystalline cellulose(MCC)is one of the cellulose derivatives produced as a result of the depolymerization of a part of cellulose to achieve high crystallinity.When implemented in other polymers,high crystallinity correlates with greater strength and stiffnes,but it can reduce the water-holding capacity.The acid concentration and hydrolysis time will affect the acquisition of crystallinity and water absorption capacity,both of which have significance as properties of hydrogel filler.The study aimed to evaluate the properties and select the MCC generated from varying the proportion of hydrochloric acid(HCl)and the appropriate hydrolysis time as a filler for film hydrogel.MCC was produced by hydrolyzing cellulose of oil palm empty fruit bunches(OPEFB)with the HCl solution at varied concentrations and periods.The results show that the longer hydrolysis times and higher HCl concentrations increase crystallinity and density while lowering yield and water absorption.The extensive acid hydrolysis reduces the amorphous area significantly,allowing the depolymerization to occur and extend the crystalline area.The morphological properties of the MCC,which are smaller but compact,indicate the presence of disintegrating and diminishing structures.A 2.5 N HCl concentration and a 45-min hydrolysis time succeed in sufficient crystallinity as well as maintaining good water absorption capacity.The treatment produced MCC with absorption capacity of 4.03±0.26 g/g,swelling capacity of 5.03±0.26 g/g,loss on drying of 1.44%±0.36,bulk and tapped density of 0.27±0.031 g/cm^(3) and 0.3±0.006 g/cm^(3),respectively,with a crystallinity index of 88.89%±4.76 and a crystallite size of 4.23±0.70 nm.The MCC generated could potentially be utilized as a hydrogel film filler,since a given proportion will be able to maintain the strength of the hydrogel,not readily dissolve but absorb water significantly.

MCC颗粒浓度及油相比例对MCC-猪油Pickering乳液制备效果的影响

为探讨微晶纤维素(microcrystalline cellulose,MCC)-猪油Pickering乳液的制备方法,分析乳化液组成对乳化效果的影响规律,以水相中MCC颗粒浓度和油相比例为变动因素,测定乳液的外观结构、乳析指数、微观结构、粒径、Zeta电位以及乳液流变特性等指标,并分析变化情况。结果表明,油相比例为50%,MCC颗粒浓度为0.4%~1.0%时,随着颗粒浓度的增加,乳液液滴粒径逐渐减小,乳析指数、Zeta电位绝对值、乳液的黏度及储能模量(G')与损耗模量(G″)逐渐增大,乳液稳定性逐渐增加。MCC颗粒浓度为1.0%,油相比例为30%~60%时,随着油相比例的增加,乳液的液滴粒径及乳析指数逐渐增加,Zeta电位绝对值呈先增大后减小趋势,乳液的黏度及储能模量(G')与损耗模量(G″)逐渐增大。因此,MCC颗粒浓度为1.0%、油相比例为50%~60%时能制备出稳定的乳化液。

Synthesis of Microcrystalline Cellulose—Polyvinyl Alcohol Stabilized Polyvinyl Acetate Emulsion

Polyvinyl alcohol (PVA) colloid stabilized Polyvinyl acetate (PVAc) based wood adhesive has poor performance in highly humid conditions. Currently, the addition of natural fillers in the wood adhesive is one of the most effective ways to enhance the performance of PVAc wood adhesive in highly moist conditions. Microcrystalline cellulose (MCC) are strong renewable, bio-based material and has great potential in a reinforcement of the polymeric matrix. Hence, the present work investigates the applicability of microcrystalline cellulose incorporated 3% and 5% in situ emulsion polymerization PVAc wood adhesives. Effect on physical, thermal and mechanical properties was studied by viscosity, pH, contact angle measurement, differential scanning calorimetry (DSC) and pencil hardness test of films. Emulsions with different proportions of MCC were prepared and the shear strength of the applied adhesive on wood was measured. The viscosity of the adhesives was increased by increasing the concentration of MCC. The mechanical properties like tensile strength of adhesives with MCC were measured by universal tensile machine (UTM). Thermal stability was studied by differential scanning calorimetry (DSC). The tensile shear strength demonstrates that MCC can improve bonding strength as compared to PVAc Homo based adhesive in the wet condition which was validated through a contact angle study. The hardness of PVAc films were also changed positively by the addition of MCC. Here, we studied the effect of the addition of different concentrations of MCC materials in situ polymerization of PVAc on their performance properties.

Effect of Water Content on Crystalline Structure of Ionic Liquids Mixture Pretreated Microcrystalline Cellulose (MCC)

Microcrystalline cellulose (MCC) was pretreated by using ionic liquids (ILs)-water mixtures solvent with solid acid catalysts. Different amount of water was considerate as the main variable. The peak shift of pretreated sample was determined by FT-IR related to the water content. The XRD was applied to characterize the change in MCC crystalline structure. Thermal decomposition technique was applied to investigate the thermal stability of pretreated MCC. The result indicated that three state of samples were occurred in pretreated MCC sample which was related the amount of water in ILs mixture system. XRD result suggested that the raw sample was distorted and transformed into a less ordered intermediate structure and the smaller crystallite size in lump state sample was obtained which could lead to lower thermal stability. This study revealed the physical chemicals properties, characteristic of molecular structures in MCC using ILs-water mixtures.

MCC接枝PVA/可溶性淀粉保鲜膜的制备

为开发全生物降解聚乙烯醇/可溶性淀粉复合膜,以聚乙烯醇和可溶性淀粉为基材,D-山梨醇为增塑剂,柠檬酸为交联剂,硅烷化接枝后的微晶纤维素为增强相,制备得到高性能全生物降解复合膜。通过对复合膜的机械性能、结构形态等进行表征,探究微晶纤维素接枝率对复合膜吸水率、溶解度、透光率、水蒸气透过率以及保鲜等性能的影响规律。结果表明:当调制的主体膜液中聚乙烯醇与可溶性淀粉质量比为82.83∶17.17、D-山梨醇质量分数为12.39%、柠檬酸质量分数为8.95%,制备得到的复合膜水蒸气透过率未符合标准且耐水性较差,而接枝2%微晶纤维素的复合膜水蒸气透过率降低了27.38%,吸水率与溶解度分别降低了11.69%和7.99%,且透光率能达到90.5%;微晶纤维素与正硅酸乙酯配比为2∶4时接枝效果最佳;当微晶纤维素质量分数为2%时复合膜热稳定性最佳,在香蕉保鲜性上提高42.1%。综上,经过一定量的微晶纤维素接枝改性的复合膜满足保鲜膜相关标准,并且保鲜性能提升明显,可作为一种可靠的全生物降解保鲜膜。

Biocomposite Films of Polylactic Acid Reinforced with Microcrystalline Cellulose from Pineapple Leaf Fibers

Poly(lactic acid)(PLA)composite films reinforced with microcrystalline cellulose(MCC)extracted from pineapple leaf fibers(PALF)were prepared by a solution casting procedure.In an attempt to improve the interaction between PLA and cellulose,two approaches were adopted;first,poly(ethylene glycol)(PEG)was used as a surfactant,and second,the cellulosic fibers were pre-treated using tert-butanol(TBA).Lignocellulosic and cellulosic substrates were characterized using Fourier transform infrared(FTIR),wide-angle X-ray scattering(WAXS),and thermogravimetrical analysis(TGA).MCC from PALF showed good thermal stability,left few residues after decomposing,and exhibited high crystallinity index.Mechanical,thermal and thermomechanical properties of the PLA composites were also evaluated.Multiple PLA endotherms were observed in composites with TBA-treated MCC due to crystal nucleation effects.The ultimate tensile strain values for all composites were lower than that of the pristine PLA.However,4 wt.%MCC content provided balanced engineering properties in terms of static and dynamic tensile properties.

Rapid and Efficient Adsorption Removal of Reactive Blue 4 from Aqueous Solution by Cross-Linked Microcrystalline Cellulose–Epichlorohydrin Polymers: Isothermal, Kinetic, and Thermodynamic Study

In this study, we modified microcrystalline cellulose by cross-linking it with epichlorohydrin to obtain a rapid and efficient adsorbent for the removal of Reactive Blue 4 dye from aqueous solution. Evidences of the cross-linking of the microcrystalline cellulose were obtained by Fourier transform infrared spectroscopy, X-ray diff raction, Brunauer–Emmett–Teller analysis, thermogravimetric analysis, and scanning electron microscopy. We investigated the eff ects of adsorbent dosage, p H, initial dye concentration, temperature, and contact time on the dye adsorption capacity. The results showed that the adsorption equilibrium time was just 20 min and the maximum adsorption capacity was 69.79 mg/g. The adsorption isotherm data fitted the Langmuir isotherm model well, and the adsorption kinetics data followed the pseudo-second-order kinetic model. The results of the thermodynamic analysis suggest that the adsorption process was spontaneous and exothermic. Recyclability experiments demonstrated the good reusability of this adsorbent. Electrostatic interaction was found to dominate the adsorption process.

Preparation of Highly Crystalline Microcrystalline Cellulose by Hydrolysis of Cellulose with Phosphotungstic Acid

Phosphotungstic acid(H_3PW_(12)O_(40), HPW), a kind of solid acid, is widely used for hydrolyzing cellulose to prepare microcrystalline cellulose(MCC). MCC is usually used in food, synthetic leather, chemical and pharmaceutical industries. The use of response surface methodology(RSM)can help avoid the random error caused by single factor experimental design,reduce test times and cost, and improve quality. The RSM was used in this study to determine the following optimal process conditions: H^+ molar quantity, 31 mmol/L; reaction temperature, 93℃; reaction time, 2 h; and solid to liquid ratio, 1∶38. Under these conditions, the crystallinity of MCC was77.4%. Thus, the use of RSM allows the preparation of MCC with higher performance and increased crystallinity.

低共熔溶剂结合球磨工艺制备MCC及其在片剂中的应用性能研究

采用氯化胆碱/甲酸(ChCl/FA)、氯化胆碱/草酸(ChCl/OA)、氯化胆碱/柠檬酸(ChCl/CA)3种低共熔溶剂(DES)处理杨木溶解浆,结合球磨处理制备微晶纤维素(MCC),探讨了不同DES体系下时间、温度对MCC聚合度、粒径等性能的影响;并以布洛芬为模型药物,将MCC作为药用辅料填充在布洛芬片中,研究了MCC粒径及用量对片剂崩解时间、累积释放率等性能的影响。结果表明,ChCl/FA体系在100℃、60 min时制备的MCC流动性最好;在不添加崩解剂的情况下,当MCC填充量为35.0%时,片剂的崩解时间为190 s,60 min内累积释放率可达86.58%,且具有较高的硬度和抗张强度,显示出DES法制备的MCC用作药用辅料具有良好的填充效果。

Obtaining and Characterization of Biodegradable Composites Reinforced with Microcrystalline Cellulose Fillers

In recent years, there has been a growing discussion about the problems related to the massive use of many synthetic plastic materials, which inevitably leads to an increase in environmental pollution caused by the inappropriate disposal of these materials. In this sense, biodegradable materials have been a subject of great interest, as they are a real alternative to replace these materials and tackle this issue. In this work, fully biodegradable composites were prepared by solution casting method. Microcrystalline cellulose (MCC) and treated microcrystalline cellulose (TMCC) were separately incorporated into biodegradable PLA and PHB matrices at ratios of 3, 5 and 7 wt% and the properties of the obtained biocomposites were evaluated by TGA, DSC, XRD and TD-NMR. From thermal analyses, it was seen that TMCC resulted in better thermal stability and 3 wt% of filler, in general, promoted a more pronounced thermal improvement. Furthermore Tg, Tc and Tm remained practically unchanged after MCC and TMCC addition. From XRD it was seen that the cellulose fillers influence in different ways the matrices, promoting increase or decrease in the degree of crystallinity. Finally, the results obtained by TD-NMR showed a decrease in the T1H values for all prepared biocomposites, indicating a good dispersion of the cellulose fillers in the matrices and pointed that the systems containing 3 wt% of cellulose fillers were the most homogeneous formulations.

Preparation of highly stable diclofenac potassium pellet with microcrystalline cellulose by extrusionespheronization

The main purpose of this study is to prepare highly stable diclofenac potassium(DP)pellet with microcrystalline cellulose(MCC)by extrusionespheronization.Using MCC,DP pellets were prepared and the stability was investigated.Related compounds of DP pellets were analyzed by High Pressure Liquid Chromatography(HPLC).After stability test of 60℃/75%RH for 10 d,the values of two main related compounds were 0.94%and 2.17%,respectively.Compatibility tests show that instability of DP was mainly caused by MCC.To improve the stability of DP in presence of MCC,different kinds of stabilizers were investigated.Upon addition of 1.5%(w/w)sodium hydroxide,the primary related compound of pellets was reduced to be 0.159%after stability test of 60℃/75%RH for 50 d.This study demonstrated that MCC induced decomposition of DP upon exposure to moisture could be prohibited by addition of sodium hydroxide.The mechanisms were discussed and residual hydroxyl free radicals in excipients were responsible for decomposition of DP.Finally,this formulation of DP is highly stable with sustained-release behavior.

Kevlar fabric reinforced polybenzoxazine composites filled with silane treated microcrystalline cellulose in the interlayers:The next generation of multi-layered armor panels

The design of astonishing combinations of benzoxazine resins with various fillers is nowadays of great interest for high quality products,especially in ballistic armors.The objective of this study is to investigate a new hybrid material prepared as multi-layered composite plate by hand lay-up technique.Different composites were manufactured from Kevlar fabrics reinforced polybenzoxazine,which was filled with silane treated microcrystalline cellulose(MCC Si)at various amounts in the interlayers.The developed materials were tested for their flexural,dynamic mechanical and ballistic performance.The aim was to highlight the effect of adding different amounts of MCC Si on the behavior of the different plates.Compared to the baseline,the dynamic mechanical and bending tests revealed an obvious decrease of the glass transition of 21℃and a notable increase in storage modulus and flexural strength of about 180%and17%,respectively,upon adding 1%MMC Si as filler.Similarly,the ballistic test exhibited an enhancement in kinetic energy absorption for which the composite supplemented with 1%MCC Si had the maximal energy absorption of 166.60 J.These results indicated that the developed panels,with interesting mechanical and ballistic features,are suitable to be employed as raw materials to produce body armor.

Fully Bio-Based Composites of Poly(Lactic Acid)Reinforced with Cellulose-Graft-Poly-(ε-Caprolactone)Copolymers

Due to the increasing demand for modified polylactide(PLA)meeting“double green”criteria,the research on sustainable plasticizers for PLA has attracted broad attentions.This study reported an open-ring polymerization method to fabricate cellulose(MCC)-g-PCL(poly(ε-caprolactone))copolymers with a fully sustainable and biodegradable component.MCC-g-PCL copolymers were synthesized,characterized,and used as green plasticizers for the PLA toughening.The results indicated that the MCC-g-PCL derivatives play an important role in the compatibility,crystallization,and toughening of the PLA/MCC-g-PCL composites.The mechanical properties of the fully bio-based PLA/MCC-g-PCL composites were optimized by adding 15 wt%MCC-g-PCL,that is,the elongation at break was 22.6%(~376%higher than that of neat PLA),the tensile strength was 47.3 MPa(comparable to that of neat PLA),and the impact strength was 26 J/m(~130%higher than that of neat PLA).DSC results indicated that MCC-g-PCL reduced the Tg of the PLA blend.When the addition amount was 15 wt%,the Tg of the blend was 58.4°C.Compared with MCC,MCC-g-PCL polyester plasticizer has better thermal stability,T5%(°C)can still be maintained above 300°C.The rheological results showed that MCC-g-PCL acted as a plasticizer,the introduction of PCL flexible chain increased the mobility of PLA molecular chain,and decreased the complex viscosity,storage modulus and loss modulus of PLA blends.The MCC-g-PCL derivatives,as a new green plastic additive,have shown an interesting prospect to prepare fully bio-based composites.

Investigation of Agave cantala-based composite fibers as prosthetic socket materials accounting for a variety of alkali and microcrystalline cellulose treatments

This study was aimed to determine the mechanical strength of composites made from Agave cantala with an unsaturated polyester matrix and microcrystalline cellulose.Cantala fiber(CF)was treated with 6%Na OH with immersion times of 0 h(UF),3 h(AK3),6 h(AK6),9 h(AK9),and12 h(AK12).Thermogravimetric analysis(TGA)analysis shows that treated CF has higher thermal stability than CF without treatment.Cantala fiber was tested by X-ray diffraction.After alkali treatment with a 6-h soaking,it had a crystallinity index of 73.65%.Scanning electron microscopy(SEM)showed that the fibers were cleaner after alkali treatment because hemicellulose,wax,and other impurities were removed.Examination of the contact angle and surface energy showed that treated CF has smaller contact angles and greater surface energy.

Adsorption behavior of free fatty acids and micro-components in rapeseed oil on alkaline microcrystalline cellulose

Alkaline microcrystalline cellulose (AMC) was used as adsorption agent in deacidification in this paper. Changes of isothermal adsorption of free fatty acids (FFA) and micro-components (α-tocopherol and β-sitosterol) in rapeseed oil on AMC were investigated. The results showed that difference in initial micro-component contents would not change adsorption characteristics of AMC to FFA. Adsorption characteristics were always as the following: Langmuir equation was more suitable to static adsorption process of AMC to FFA than Freundlich equation; moderate temperature (30-40oC) was advantageous to adsorption; adsorption was a preferential one. The highest retention rate of α-tocopherol and β-sitosterol during absorptive deacidification by AMC were 99.5% and 91.5% respectively. Therefore, AMC was suitable for adsorption deacidification application of rapeseed oil.

微晶纤维素改性聚乙烯醇复合膜的性能及其作用机理

从麦秆中提取微晶纤维素(MCC),将其加入到聚乙烯醇(PVA)中对其进行改性,通过共混、流延制备了PVA/MCC复合膜。研究了NaOH用量对麦杆纤维素收率的影响,以及MCC用量对复合膜力学性能和热性能的影响,并考察了PVA/MCC复合膜的结构、微观形貌。结果表明:当NaOH质量分数为4%时,麦杆纤维素收率最大,为53.9%;加入MCC后,PVA/MCC复合膜的热稳定性提高;复合膜的力学性能随着MCC用量的增加先上升后下降,当MCC用量为9%(w)时,复合膜的拉伸强度及断裂标称应变均最大,分别较纯PVA提升了约191%,636%;MCC用量为12%(w)时,MCC在PVA中团聚,形成明显的“海岛”结构,导致复合膜的力学性能下降。

花生壳微晶纤维素改性聚乳酸的性能及机理

花生壳采用碱解、酸解、脱色等处理后制得微晶纤维素(MCC),将其作为填料加入到聚乳酸(PLA)中,通过溶液流涎成膜的方法制得不同MCC含量的MCC/PLA复合膜。分析了碱解过程中氢氧化钠浓度对MCC收率的影响、MCC含量对MCC/PLA复合膜性能的影响及其作用机理。利用傅里叶变换红外光谱仪(FTIR)、差示扫描量热仪(DSC)、扫描电子显微镜(SEM)、万能力学试验机等对MCC及MCC/PLA复合膜结构及性能进行表征和分析。结果表明,花生壳通过碱解、酸解、脱色等处理,将木质素等物质大量去除,制得MCC;MCC的加入,影响了PLA结晶结构的规整度及完善程度,降低了复合膜的熔融温度;随着MCC含量的增加,MCC/PLA复合膜的拉伸强度和断裂伸长率呈先增加后降低的趋势,均大于纯PLA的拉伸强度和断裂伸长率。当MCC的含量为5.6%时,MCC/PLA复合膜的拉伸强度为36.5 MPa,断裂伸长率达到最大值1.7%,与纯PLA相比,分别提高了52.1%和30.8%;SEM结果表明,该含量的MCC在PLA中分散均匀,复合膜光滑平整。

均相体系中改性纤维素的制备及其对亚甲基蓝的吸附性能研究

为了开发低成本、环境友好的吸附材料用于吸附、分离水中的染料离子,在均相体系中,以纤维素为基材、过硫酸钾为引发剂、甲基丙烯酸缩水甘油酯(GMA)为接枝单体,制备了纤维素接枝共聚物Cell-g-PGMA,并通过FT-IR、XRD和TGA对接枝共聚物进行了表征。系统研究了接枝时间、温度、单体用量和引发剂用量对接枝率的影响。同时在不同吸附时间、温度、吸附剂用量和初始浓度下考察了Cell-g-PGMA对亚甲基蓝(MB)离子的吸附性能。研究表明,该吸附剂对MB表现出优异的吸附性能,理论最大吸附量为271.39mg/g,吸附过程符合准二级动力学模型和Langmuir吸附等温线。

丙基噁唑啉改性微晶纤维素增强增韧聚乳酸的研究

利用丙基唑啉(POZ)对微晶纤维素(MCC)进行化学改性得到酰胺化微晶纤维素(AD-MCC),AD-MCC与聚乳酸(PLA)通过熔融共混法制备AD-MCC/PLA复合材料。利用FT-IR、SEM、XRD、TG、万能试验机等研究了AD-MCC的制备条件,并考察了AD-MCC添加质量分数对AD-MCC/PLA的性能影响。结果表明,在甲醇钠催化下120℃反应8 h,可得到POZ接枝率为31.47%的AD-MCC;AD-MCC提高了MCC与PLA的相容性,使PLA力学性能显著提高;添加2.5%AD-MCC可使PLA复合材料的拉伸强度提高26%,断裂伸长率提高61%,冲击强度提高57%。

纳米氧化物@微晶纤维素的辐射制备及其对三氯乙酸的吸附去除

作为饮用水消毒常见的非挥发性副产物,三氯乙酸(Trichloroacetic acid,TCA)对人体具有致癌的危害性。本研究通过预辐射接枝包埋法成功制备了4种纳米氧化物@微晶纤维素基吸附剂(P25@微晶纤维素、SiO_(2)@微晶纤维素(MCC-g-GMA@SiO_(2))、Fe_(3)O_(4)@微晶纤维素和Fe_(2)O_(3)@微晶纤维素),探究其对饮用水中TCA的去除率。利用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、热重(TG)分析、扫描电子显微镜(SEM)等表征手段对材料的微区形貌、表面结构及吸附性能进行了表征与测试,并系统对比探讨了不同单体浓度、包埋物浓度、吸收剂量等对其增重率的影响。通过对4种包埋的纳米氧化物进行吸附实验对比,得到了完整的静态吸附平衡曲线。结果表明:SiO_(2)@微晶纤维素性能明显优于其他3种吸附剂,且单体浓度体积百分数在30%、包埋物质量百分数为4%、吸收剂量在60 kGy时,对饮用水中TCA的去除率达到83.27%。该系列吸附材料在饮用水净化领域具有重要的应用价值。