抗老化剂改善竹粉/聚丙烯发泡复合材料的自然老化性能

为探索木塑复合材料的老化规律,改善木塑产品的老化性能,该文以化学发泡法制备的竹粉/聚丙烯(polypropylene,PP)发泡复合材料为研究对象,采用户外自然老化方式,研究自然老化对发泡复合材料材色、弯曲蠕变性能、流变性能的影响;同时为改善发泡复合材料的老化性能,研究了抗老化剂对发泡复合材料自然老化性能的影响。结果表明:抗氧化剂B225和抗紫外线剂UV770均可改善复合材料的自然老化变色,减缓复合材料的老化褪色,提高复合材料老化后的弯曲蠕变性能和流变性能。在提高复合材料材色稳定性和初始刚性方面,添加质量分数为0.6%B225的效果较优,其次是添加0.3%B225+0.3%UV770、最后是添加0.6%UV770;而添加0.3%B225+0.3%UV770的复合材料,其流变性能稳定性较佳。自然老化12个月后,未添加抗老化剂的复合材料产生的色差△E*为22.8,而添加0.6%B225、0.6%UV770、0.3%B225+0.3%UV770的复合材料,其△E*分别为14.2、17.6和16.8。自然老化12个月后,添加抗老化剂的复合材料,其产生的蠕变应变减小且弯曲性能保留率增大。动态频率扫描结果显示,自然老化会降低复合材料的储能模量、损耗模量、复数黏度和平均分子量,缩短松弛时间;添加抗老化剂不仅可提高复合材料的初始流变性能,而且可改善复合材料的流变性能稳定性。研究结果为进一步探索木(竹)塑发泡复合材料的老化规律及木塑生产实践提供数据和理论参考。     

适宜共混速度改善低密度聚乙烯/竹粉复合材料力学与流变性能

该文主要研究共混速度对(low density polyethylene,LDPE)/竹粉木塑复合材料、流变性能和吸水率的影响。采用熔融共混方法制备LDPE/竹粉复合材料,通过旋转流变仪、扫描电镜(scanning electron microscope,SEM)和材料试验机等详细研究了共混速度(40,75和100 r/min)对LDPE/竹粉复合材料的复合材料动态力学性能、形态、吸水率和力学性能的影响。在LDPE/竹粉复合材料,LDPE、增容剂马来酸酐接枝聚乙烯(maleic anhydride grafted polyethylene,MAPE)和竹粉的质量比控制在65∶5∶30。共混温度和时间分别设定为170℃和10 min。结果表明,添加竹粉可有效增强LDPE的力学性能。LDPE/竹粉复合材料的拉伸强度和弯曲强度随着共混速度的增加而呈现下降趋势,但是与纯LDPE相比,LDPE/竹粉复合材料(40 r/min)的拉伸强度和弯曲强度分别增加了28%和115%;弯曲模量从48.45 MPa降低到40.75 MPa。与LDPE相比,LDPE/竹粉复合材料(40 r/min)的弯曲模量最高增加了238%;缺口冲击强度则从12.8 k J/m2提高到18.27 k J/m2,但仍低于纯LDPE。在相同频率下(1.0 Hz),随着共混速度的增加,LDPE/竹粉复合材料的储能模量和复数黏度也逐渐下降,加工性能得到了改善;同时复合材料的吸水率也从0.89%(40 r/min)下降至0.59%(100 r/min)。SEM结果表明,竹粉能均匀分布在LDPE中,提高共混速度使得竹粉表面被大量树脂覆盖,改善了界面性能,使得材料断裂面产生大量的塑性形变,提高了材料韧性和冲击强度。试验结果证实共混速度为100 r/min时,LDPE/竹粉复合材料具有较好的冲击强度和较低的吸水率,这为木塑复合材料力学性能和吸水率的改善提供有意借鉴。     

竹粉/聚丙烯发泡复合材料的增韧效果

为研发可代替聚丙烯(polypropylene,PP)应用于汽车内饰件的木塑复合材料,减少白色污染,节约化石能源,同时提高木塑复合材料的附加值,拓宽其应用领域。该文以注塑法制备竹粉/聚丙烯发泡复合材料,并分别采用乙烯-1-辛烯共聚物(polyolefin elastomer,POE)和马来酸酐接枝POE(maleic anhydride grafted polyolefin elastomer,POE-g-MAH)增韧复合材料。研究了增韧填料对发泡复合材料力学性能的影响,用环境扫描电镜(environmental scanning electronic microscopy,ESEM)对复合材料的冲击断面进行观察,并进行了频率扫描的动态流变测试。结果表明:添加POE和POE-g-MAH在略微降低材料拉伸和弯曲强度的同时,可明显提高材料的缺口冲击强度,二者最佳用量分别为15%和8%;8%POE-g-MAH增韧的复合材料的缺口冲击强度为8.55kJ/m2,提高了35.7%,可很好地应用于汽车内饰件。ESEM显示,增韧后,复合材料的断裂形式转变为韧性断裂。动态频率扫描结果显示,POE对复合材料流变性能的影响较小,而POE-g-MAH增韧的复合材料的储能模量和复数黏度明显增大,且"第二平台"现象更为明显。     

稻壳及硅烷添加量对木塑复合材料力学性能的影响

采用一步法连续挤出技术将稻壳粉和聚乙烯进行熔融复合制备复合材料,用硅烷作为偶联剂,研究了稻壳粉与硅烷添加量对复合材料力学性能的影响。实验结果表明：稻壳和硅烷添加量对复合材料界面有很大影响,复合材料的冲击强度、弯曲强度以及抗拉强度随稻壳添加量的增加而明显下降。添加适量的偶联剂可以改善复合材料界面相容性和稻壳在复合体系中分散均匀性,从而改善力学性能。     

竹粉/聚丙烯发泡复合材料加速老化性能的研究

为改善木塑复合材料密度大、韧性差的缺陷,采用注塑法制备竹粉/聚丙烯(polypropylene,PP)发泡复合材料;同时为加强木塑材料的生产和质量管理,采用氙灯加速老化方式,研究老化对发泡复合材料力学性能、材色、流变性能的影响,并采用环境扫描电镜(environmental scanning electronic microscopy,ESEM)和傅里叶红外光谱(Fourier transform infrared spectrum,FTIR)对材料进行分析。结果表明:历时1 200 h氙灯加速老化后,材料的弯曲强度、弯曲模量和缺口冲击强度的保留率仅分别为79.4%、68.3%和75.6%;产生的色差ΔE*和白度变化值ΔL*分别为49.0和48.4。频率扫描结果显示,老化后,复合材料的模量和黏度下降。ESEM显示,老化后材料表面出现孔洞和裂缝,且部分竹粉暴露在材料表面。FTIR结果表明,老化过程中,复合材料发生了光氧化降解反应。该研究可为进一步探索竹塑发泡复合材料的老化规律,制定产品标准提供试验数据和理论参考。     

不同表面处理麦秸秆对木塑复合材料性能的影响

为提高麦秸秆纤维与聚丙烯(polypropylene,PP)基体的界面结合力,采用复合处理法对麦秸秆纤维进行表面处理:先分别用NaOH、乙酸溶液浸泡、水热处理、蒸汽爆破和微波等方法对麦秸秆纤维进行预处理,再复合偶联剂法处理麦秸秆纤维;用熔融共混、模压成型方法制备麦秸秆/废弃PP木塑复合材料,探讨了麦秸秆不同表面处理方法制备PP木塑复合材料力学性能和吸湿吸水性能;用体视显微镜对不同处理的麦秸秆及木塑复合材料拉伸断面进行观察。结果表明:经复合处理的麦秸秆与PP木塑复合材料力学性能和吸湿吸水性能均优于单纯使用偶联剂处理的麦秸秆与PP木塑复合材料;NaOH和乙酸复合处理的复合材料力学性能和抗吸湿吸水性能较好,水热和蒸汽爆破复合处理的复合材料次之。麦秸秆经复合处理后,表面变粗糙,秸秆纤维和PP基体的界面黏合性得到改善。该文研究结果对通过麦秸秆纤维表面处理提高麦秸秆/废弃PP木塑复合材料的性能有重要的实际意义。     

不同模压成型条件下聚丙烯木塑复合材料性能

为利用农林废弃物和环境保护,以稻秸秆粉、稻壳粉、木粉、竹粉及稻秸秆与木粉的混合粉为填充材料,以PP膜为基体材料,采用层铺模压和混炼模压2种成型方法制备不同填料PP木塑复合材料,对木塑复合材料力学性能和吸湿吸水性能进行测试和分析,用体视显微镜对复合材料拉伸断面进行观察。结果表明,混炼模压成型木塑复合材料力学性能和抗吸湿吸水性能均优于层铺模压木塑复合材料,且混炼模压PP木塑复合材料填充材料与基体之间混合均匀,两相界面之间结合良好,层铺模压PP木塑复合材料有植物纤维粉和PP基体堆积现象。稻秸秆粉制备的PP木塑复合材料综合力学性能较好,竹粉PP木塑复合材料力学性能较差,模压前混炼对PP木塑复合材料吸湿、吸水性有较大的改善作用。该研究可为利用废旧塑料膜作基体制备木塑复合材料的研究与生产提供参考。     

适宜薄膜含量提高棉秆/塑料定向复合板力学和吸水性能

为了有效利用棉秆资源,制备高性能的生物质秸秆人造板,该文以等规聚丙烯和高密度聚乙烯薄膜为填充材料,以长棉秆束为基体材料,采用定向分层铺装方法,热压制备了不同薄膜含量的棉秆/塑料定向复合板,测试了复合板的物理力学性能,用扫描电子显微镜观察了复合板的微观结构。结果表明,等规聚丙烯基复合板物理力学性能优于高密度聚乙烯基复合板,且当等规聚丙烯薄膜质量分数为15%时,复合板性能较佳,在此条件下,复合板的静曲强度、弹性模量、内结合强度、吸水厚度膨胀率和吸水率分别为60.60 MPa、5074.4 MPa、1.48 MPa、2.53%和18.60%。复合板中棉秆纤维和塑料薄膜接合界面存在机械啮合结构。该研究可为利用农业生物质秸秆和塑料薄膜制备木塑复合材料提供参考。     

竹粉接枝改性提高竹塑复合材料的力学性能

为提高竹粉与聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯（polyethylene terephthalate glycol,PETG）基体的界面结合力,拓宽其应用领域,该论文以2-溴异丁酰溴修饰过的竹粉为大分子引发剂,FeCl3·6H2O/三苯基膦为催化体系,抗坏血酸为还原剂,采用电子活化再生原子转移自由基聚合法在竹粉表面接枝聚甲基丙烯酸甲酯,并通过红外光谱分析竹粉改性前后的表面化学基团变化。利用熔融共混、模压成型方法制备竹粉/PETG 竹塑复合材料。研究了竹粉接枝前后竹塑复合材料的弯曲性能,考察了竹粉改性对竹塑复合材料动态热力学性能的影响,并利用环境扫描电镜对竹粉/PETG 复合材料冲击断面进行观察。研究结果表明：接枝前后竹粉的红外光谱的显著变化证实了接枝反应的发生,聚甲基丙烯酸甲酯（polymethyl methacrylate,PMMA）成功地接枝到竹粉表面;与未改性的竹粉相比,改性后竹粉填充PETG复合材料的弯曲性能有较大提高,如竹粉质量分数为30%复合材料改性后弯曲强度提高了16%;动态热机械分析可知,竹粉经改性后其复合材料玻璃化转变温度和损耗角正切均有所降低,且在升温过程中仅出现一个损耗峰,表明竹粉表面接枝的PMMA可以充当竹粉与PETG的增容剂;环境扫描电子显微镜显示,竹粉经接枝改性后,竹粉能均匀分散在PETG基体中,竹粉与PETG基体之间的相容性得到了有效改善,界面结合良好。研究结果对通过竹粉表面处理提高竹粉/PETG竹塑复合材料的性能有重要的实际意义。     

木塑层合板的制备工艺及抗弯性能

为了弥补常规木塑复合材料的力学性能较低的不足,满足木塑复合材料在结构领域中的应用要求,试验以国产速生杨木为研究对象,以聚乙烯和聚丙烯塑料合金为粘结剂,采用平压法制备了结构用木塑层合板。通过研究热压温度、木材塑料质量比和马来酸酐添加量等3个因素对木塑层合板胶合性能的影响,以优化其制备工艺;在此基础上,进一步研究和分析了木塑层合板抗弯性能的影响因素及其作用机理。结果表明,拉伸剪切荷载作用下,偶联剂的介入,木塑层合板的破坏模式由空白试件的界面分层剥离转变为木材拉伸断裂;试验范围内,温度为180℃、木材塑料质量比为3/2、马来酸酐添加量为4%时木塑层合板的胶合性能较优,胶合强度达到0.98MPa,与未添加偶联剂的空白试件相比,胶合强度提高16.7%;采用层积法制备工艺,木塑层合板的抗弯性能能够达到结构用材的要求;密度0.6和0.8 g/cm3时,木塑层合板随着板材密度和木材塑料质量比的提高,静曲强度增大、抗弯弹性模量降低,木材单层板形态完整;密度为1.0 g/cm3时,随着木材塑料质量比的提高,木塑层合板静曲强度降低、抗弯弹性模量提高,当木材塑料质量比为3∶3时,木塑层合板中木材横纹出现大量不连续裂纹,木材的形态完整性下降;热压温度190℃、木材塑料质量比3/2和3/3、马来酸酐添加量为4%、板材密度为0.8 g/cm3时,制备的木塑层合板抗弯性能较优,能够达到100E等级的要求;结果可为木塑层合板在结构领域中的应用提供参考。     

Fortification of Wheat Dough with Calcium and Magnesium Ions Affects Empirical Rheological Properties

This study evaluated the influence of calcium and magnesium ions on the empirical rheological properties of wheat flour to verify possible effects of these ions on processing because, in addition to their nutritional importance, they are also responsible for water hardness. Calcium (0–1.30 g/100 g) and magnesium (0–0.34 g/100 g) ions from sulfate salts were added to wheat flour, according to a central composite rotatable design. The farinograph and extensigraph properties of wheat flour and its mixtures were evaluated. The results were analyzed by response surface methodology. Calcium ions stood out for increasing water absorption, decreasing mixing stability, and producing a delayed effect on dough extensibility (reduced at 135 min). Magnesium ions influenced most flour rheological properties in a similar manner to oxidizing agents (increased dough stability, increased resistance to extension, and reduced extensibility), thus proving to be a possible replacement agent for these additives. An interaction effect of the combined calcium and magnesium ions was observed on dough development time. The results showed that effects on processing can occur when wheat flour fortification is made, and adaptations on wheat flour specifications, product formulation, and processing parameters may be required.     

纳米CaCO3增强竹浆纤维/环氧树脂复合材料的动态力学性能

为探索碳酸钙(CaCO_3)无机颗粒界面增强机理,建立竹纤维表面微纳米颗粒的附载与界面增强技术的内在联系,该论文以竹浆纤维(bamboo pulp fiber,BPF)和环氧树脂为主要材料,采用纳米CaCO_3浸渍改性工艺,通过真空辅助树脂浸注技术制备BPF/环氧树脂复合材料,利用动态力学分析仪对其动态热机械性能和界面性能进行研究。结果表明:测试频率为单频(1Hz)时,在–20~120℃,纳米CaCO_3浸渍改性竹浆纤维(BPF treated by impregnation modification,IMBPF)增强环氧树脂复合材料的最大储能模量是BPF/环氧树脂复合材料的1.3倍;测试频率为多频(1,2,5,10和20 Hz)时,频率对BPF/环氧树脂复合材料和IMBPF/环氧树脂复合材料的影响规律相同,储能模量,损耗模量和损耗因子均随频率的增加而增加且逐渐向高温方向移动。BPF/环氧树脂复合材料和IMBPF/环氧树脂复合材料的玻璃化转变温度均随频率的增加而升高,而测试频率对损耗因子影响不大;IMBPF/环氧树脂复合材料的玻璃化转变表观活化能(369.0kJ/mol)低于BPF/环氧树脂复合材料(495.8 kJ/mol),但IMBPF/环氧树脂复合材料的频率和玻璃化转变温度倒数的相关性(决定系数0.987 6)优于对照样(决定系数0.965 9);在–20℃、40℃和100℃时,IMBPF/环氧树脂复合材料的储能模量对频率的依赖性高于对照样;纳米CaCO_3浸渍改性技术可改善复合材料的界面性能,从而为纳米增强复合材料的研究提供理论依据。     

Effect of l‐Cysteine on the Rheological Properties of Wheat Flour

Extrudate expansion of cereal‐based products is largely dependent on the molecular interactions and structural transformations that proteins undergo during extrusion processing. Such changes strongly influence the characteristic rheological properties of the melt. It is possible to modify rheological properties of wheat flour during extrusion processing, in particular shear viscosity, with cysteine. The objective of this work was to further develop an understanding of the molecular interactions and structural transformations of wheat flour from dynamic oscillatory rheological measurements. Temperature and frequency sweeps were conducted in the linear viscoelastic range of the material. Changes in the storage modulus (G′), the loss modulus (G″) and the loss tangent (tan δ) of 25% moisture wheat flour disks as a function of cysteine concentration (0–0.75%) were monitored. Molecular weight between cross‐links (M_c) and the number of cross‐links (N_c) per glutenin molecule were determined from frequency sweep data. Increasing cysteine concentration broke cross‐links by decreasing G′ maximum and increasing tan δ values. Molecular weight between cross‐links increased and the number of cross‐links decreased. G′ values from temperature sweeps showed a similar trend. This information leads to a better understanding of the viscoelastic behavior of wheat flour doughs during extrusion cooking and elucidation of protein‐protein reaction mechanisms and other interactions in extruded cereal‐based snack foods.     

Characterization of Dynamic Viscoelastic Behavior of Wheat Flour Doughs at Different Moisture Contents

Three different flours were examined to study the influence of moisture content on the dynamic viscoelastic behavior of wheat flour dough. Doughs with moisture contents varying from 43 to 58% were submitted to dynamic testing using a mechanical spectrometer operating in frequency sweep mode, obtaining information about rheological response in the linear viscoelastic range. To characterize the influence of moisture content on the dynamic viscoelastic behavior of wheat flour dough, some hypotheses regarding the functional role of the water molecules were verified by applying reduction procedures of the rheological curves. By shifting the rheological curves along the vertical axis, it was possible to verify that varying the moisture content of the doughs not only changed dynamic properties but also modified viscoelastic response. By applying a reduction procedure similar to that used to estimate the constants of the Williams, Landel, and Ferry equation, we demonstrated that not only did the viscoelastic response of doughs vary, but that water molecules interfere with the dynamic by which relaxation phenomena take place. Finally, we proved that the rheological behavior of flour dough is similar to that of concentrated polymer solutions, and that it can be characterized by using a double reduction procedure, shifting the rheological curves along the vertical and horizontal axes, and obtaining a master curve that can be considered inherently characteristic of viscoelastic behavior.     

含氢硅油改性稀土荧光竹塑复合材料的耐水性

为提高稀土荧光竹塑复合材料的耐水性能,拓宽其应用范围。利用含氢硅油改性竹粉和铝酸锶荧光粉表面,熔融共混,注塑成型的方法制备稀土荧光竹塑复合材料。通过接触角测量仪、荧光分光光度计、电子万能试验机、扫描电镜等仪器研究含氢硅油改性对复合材料接触角、吸水性能、发光性能和力学性能的影响。结果表明：未改性复合材料表面具有亲水性,改性复合材料表面具有疏水性。相比于未改性复合材料,改性复合材料的吸水率和吸水厚度膨胀率较低。经11 d水浸泡,改性复合材料的相对发光强度下降28.82%显著低于（P＜0.05）未改性复合材料的46.40%,改性复合材料的发光性能耐水性更好。随着浸水时间的延长,复合材料的弯曲强度、弯曲模量、拉伸强度均下降并趋于稳定,冲击强度先增大后减小,然后趋于稳定,与未改性复合材料相比,改性复合材料的弯曲强度、弯曲模量、拉伸强度的下降率较低（P＜0.05）,改性复合材料的力学性能遇水更稳定。扫描电镜显示,改性复合材料中荧光粉和竹粉在基体中分散较均匀、团聚减少、界面黏合强度改善。复合材料经含氢硅油改性后,游离羟基数量减小,羟基吸收峰向低波数移动,在1 387.75 cm-1处出现Si-CH3的特征吸收峰,表明含氢硅油与竹纤维和荧光粉表面羟基发生了化学反应,研究结果对提高稀土荧光竹塑复合材料的耐水性具有实际意义。     

Effects of Salt and Alkaline Reagents on Dynamic Rheological Properties of Raw Oriental Wheat Noodles

To gain further understanding of the functionality of ingredients in oriental wheat noodles, the rheological properties of raw noodles made using high protein (Red Bicycle) or low protein (Sandow) wheat flours and various additives (salt or alkaline reagents at concentrations of 0, 0.1, 0.5, 1.0, 2.0, 3.0, and 4.0%) were investigated using frequency sweep and temperature sweep oscillatory tests. Generally, both the elastic modulus(G′) and viscous modulus (G″) of raw noodles increased when various levels of salt or alkaline (kansui and NaOH) reagents were included in the formulation, with the exception of Red Bicycle noodles where the G″ was not significantly affected by the salt. The G′was significantly decreased in the presence of sodium chloride at concentrations ≤4.0% and kansui at <0.5%. The change in rheological properties of raw noodles was related to the wheat flour quality, type, level of additive, and frequency. The G′, G″, phase angle, and complex viscosity changed in a similar pattern when raw noodles were heated from 25 to 100°C. These parameters decreased initially with increasing temperature until they reached a valley and then increased either to a plateau or continuously in noodles containing kansui. The appearance of valley points at 75.5 and 77.2°C during heating of Sandow and Red Bicycle noodles containing salt, and 89.4, and 83.2°C during heating of Sandow and Red Bicycle noodles containing kansui, respectively, was not associated with starch gelatinization as determined using differential scanning calorimetry. The continuous increase in G′, G″, and complex viscosity observed with noodles containing kansui during the hold period at 100°C was attributed to the high pH environment and not to the inactivation of α‐amylase.     

芯壳结构竹塑复合材料断口冲击强度的分形表征

为了定量表征不同壳层材料对芯壳结构竹塑复合材料冲击断口复杂程度的影响,以造纸剩余物竹屑和高密度聚乙烯(high density polyethylene,HDPE)作为芯层材料,以纯HDPE、竹浆纤维/HDPE、纳米碳酸钙/HDPE和白泥/HDPE分别作为壳层材料,采用熔融共挤工艺制备芯壳结构竹塑复合材料。在室温(23℃)环境下,测试了复合材料无缺口冲击强度,采用扫描电镜对4种不同壳层材料断口进行形貌分析,基于分形理论和图像处理技术,运用像素点法计算了复合材料的冲击断口表面分形维数,考察了复合材料断口表面分形维数和冲击强度的关系。结果表明,不同壳层材料的芯壳结构竹塑复合材料冲击断口表面分形维数存在一定差异,壳层为HDPE的复合材料断口表面分形维数最大,为2.2204,壳层为白泥/HDPE的分形维数最小,为2.2075。不同壳层复合材料冲击断口表面分形维数拟合曲线的决定系数均大于0.98,说明复合材料断口表面分形特征显著。并且,复合材料断口表面分形维数与冲击强度之间拟合曲线的决定系数为0.9857,近似呈指数函数关系。研究结果为进一步深入研究芯壳结构竹塑复合材料的表面微观结构提供参考。