室温固化高低温使用环氧胶粘剂的制备与性能

研究了一种在-150℃~100℃宽温度范围具有较高剪切和剥离强度,并且能够承受液氮温度(-196℃)~150℃冷热冲击的室温固化环氧胶粘剂体系。探讨了促进剂2,3,4-三(二甲胺基甲基)苯酚(DMP30)的最佳用量,考察了不同固化时间及后固化工艺对胶粘剂固化度、玻璃化转变温度和力学性能的影响。结果表明,适量DMP30的添加有利于提高固化物的力学性能,后固化可以提高固化物的固化度和拉伸强度,但对于已处于玻璃态的固化物的性能影响很小。当胶粘剂的本体强度达到一定值后,体系固化度和玻璃化转变温度与其剪切强度的关系不大,后固化对其本体强度的提升不能带来粘接强度的相应明显提高。     

紫外光固化超支化聚氨酯丙烯酸酯的制备及性能

采用异佛尔酮二异氰酸酯(IPDI)或甲苯二异氰酸酯(TDI)与聚四氢呋喃醚二醇(PTMG)反应生成线型的分子结构,再加入甘油得到具有超支化结构的聚氨酯预聚体,接枝上丙烯酸酯制得超支化聚氨酯丙烯酸酯(PUA)。通过红外分析、核磁共振氢谱、凝胶渗透色谱和热重分析等对PUA的结构和性能进行了表征,讨论了甘油和丙烯酸酯的加入比例、反应时间和温度等因素对PUA性能的影响。研究结果表明,合成了预期结构的超支化PUA;10 min左右即可快速UV固化成1 mm厚膜;随着交联剂含量的增加,2种PUA的拉伸强度均达到50 MPa以上;拉伸剪切强度接近0.8 MPa;固化膜沸水中的吸水率低于5%,丙酮中的溶胀率低于300%,在酸或碱溶液中浸泡7 d,无起泡、起皱和发白等现象。     

增塑剂DOP对紫外光固化胶粘剂性能的影响

采用邻苯二甲酸二辛酯(DOP)做增塑剂,加入到聚氨酯丙烯酸酯紫外光(UV)固化胶粘剂中,发现DOP对胶粘剂具有良好的稀释增塑作用。通过透射电镜(TEM)照片发现,部分增塑剂DOP以微小的团聚体分散在固化后的体系当中。DOP的加入能降低胶粘剂的初始施工黏度,同时胶粘剂的拉伸剪切强度降低,而不均匀扯离强度增大。DOP的加入使胶粘剂固化后的交联密度降低,而玻璃化温度(Tg)先明显降低后又有所升高。胶粘剂固化后放置一段时间,其强度还会上升。     

无机胶粘剂的套接压缩剪切强度

研究了调胶比、固化温度及固化时间、粘接表面粗糙度和配合间隙等因素对氧化铜-磷酸铝无机胶粘剂套接压缩剪切强度的影响。试验结果表明:调胶比在4~4.5g/mL,轴孔配合间隙在0.2~0.4mm,固化温度120℃左右,固化时间为3h时既能获得良好粘接性能,又能获得充裕的粘接操作时间;同时粘接表面越粗糙,套接压缩剪切强度越高。     

响应面优化法研究果糖间苯二酚树脂胶粘剂的合成

以高果糖浆代替甲醛,在碱性条件下合成了一种绿色环保型果糖间苯二酚树脂胶粘剂。用响应面优化法对果糖间苯二酚树脂的合成条件进行了优化,以树脂黏度为考察指标,根据Box-Benhnken的中心组合实验设计原理,对实验进行设计并对结果进行了分析。研究了温度、时间和催化剂用量对反应的综合影响,得出最佳工艺条件为:反应温度61.97℃、反应时间5.24h、催化剂质量分数6.21%。在此条件下,树脂的黏度为285.523 mPa.s,测得所研制的胶粘剂的拉伸强度达到33.1 MPa。     

秸秆液化物环氧树脂胶粘剂的制备与表征

以苯酚液化秸秆为原料,与环氧氯丙烷反应,制得一种以秸秆液化物为基材的新型环氧树脂。考察了液比(苯酚与秸秆的质量比)、反应温度和反应时间对液化反应的影响,结果表明,液比为4,反应温度为150℃,反应时间为1h时,残渣率为1.97%。通过正交试验确定了合成环氧树脂的最佳工艺:秸秆液化物质量与环氧氯丙烷体积比为4∶20,反应温度为80℃,反应时间为3h,催化剂用量为5.0%,胶粘剂剪切强度可达到3.18MPa。通过红外光谱和凝胶渗透色谱测定了环氧树脂的结构和相对分子量分布;用热重分析法测定了环氧树脂胶粘剂的热稳定性,其稳定性较好。     

增塑剂乙酰聚合甘油不饱和脂肪酸多酯的合成及应用

以自制二聚甘油和油酸为原料进行酯化反应合成聚甘油不饱和脂肪酸多酯,再与乙酸酐反应得到乙酰聚甘油不饱和脂肪酸多酯。采用单因素试验研究反应温度、反应时间、聚甘油与油酸摩尔比、催化剂用量对酯化率的影响,确定最优合成工艺条件为反应温度215℃、反应时间3 h、油酸与聚甘油摩尔比4∶1、催化剂用量1.5%,该条件下酯化率为87.7%。采用红外光谱、热重分析、凝胶渗透色谱对产物进行了表征。热重分析表明当温度达到500℃时,残留质量为0.21%;凝胶渗透色谱分析结果表明,珚Mn为2354,珚Mw为3050,珚Mz为6549,相对分子质量分布指数为1.2957;拉伸强度为(22.69±3.10)MPa,断裂伸长率为(65.21±5.25)%。     

3,3',4,4'-联苯四胺改性邻苯二甲腈树脂及其复合材料性能

采用3,3’,4,4’-联苯四胺(LBS)与联苯型邻苯二甲腈树脂(BPh)进行预聚反应制备改性联苯型邻苯二甲腈树脂预聚物(BLBS)。利用红外光谱法、差示扫描量热仪、旋转流变仪和热重分析对BLBS的固化行为、流变性能和耐温性能进行研究。结果表明,BLBS最低可在240℃前开始固化,但仍需要较高的温度才能固化完全;BLBS-3固化物在氮气和空气氛围中的质量损失5%时的温度(T_d5)分别为549.4℃和555.6℃。石英纤维增强BLBS复合材料(QF/BLBS)具有优异的力学性能和耐热性能,玻璃化转变温度(T_g)大于500°C,室温弯曲强度和层间剪切强度分别为711.5 MPa和48.5 MPa,400℃热处理2 h后弯曲强度和层间剪切强度分别为680.5 MPa和31.3 MPa。     

离子液体与杉木粉对酚醛胶粘剂性能的影响

制备了离子液体/杉木粉/酚醛树脂的复合胶粘剂,用DSC、FTIR和TGA分别对其固化温度、化学结构及热稳定性进行测试分析,研究了木粉和离子液体对复合胶粘剂性能的影响.结果表明,木粉能有效降低胶粘剂的游离醛含量,离子液体可以大幅度提高胶粘剂的胶合性能.与普通酚醛胶相比,当离子液体与木粉质量比为10:1时,复合胶粘剂游离醛从1.76%降低到0.24%,拉伸剪切强度从2.16 MPa提高到5.39 MPa,且固化后不龟裂,透明度较高.TGA结果表明复合胶的热分解温度提高,但残碳率降低.分析了被离子液体溶解的木粉对游离醛的捕捉作用及离子液体对胶合性能的贡献.     

耐高温聚氨酯改性TDE-85/E-51环氧树脂胶粘剂的制备和性能

以混合芳胺为固化剂,通过聚氨酯(PU)对4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯(TDE-85)与二酚基丙烷缩水甘油醚(E-51)环氧树脂的改性,制备了一种高强高韧的耐高温环氧树脂结构胶粘剂。通过改变E-51、TDE-85、PU及固化剂之间的配比,探讨了各个组分对胶粘剂力学性能的影响。通过SEM分析,研究了PU增韧环氧树脂的机理。结果表明,TDE-85和E-51的配比为1∶1,PU添加量为环氧树脂的19%,芳胺固化剂添加量为20%时,胶粘剂具有最佳的耐热性和力学性能。制备的PU改性TDE-85/E-51结构胶粘剂室温拉伸剪切强度达到25.81 MPa,160℃高温拉伸剪切强度为12.85 MPa,剥离强度达到51.68 N/cm。     

固化剂混掺对高温下CFRP板-钢板界面黏结性能的影响

针对单一固化剂难以兼顾耐热性和韧性的不足,研究了耐热性能较好的缩胺105和韧性较好的聚醚胺D230两种固化剂混掺对纳米SiO₂环氧胶黏剂玻璃转变温度及高温下基本力学性能的影响。按一定固化条件制作了30个胶黏剂拉伸试件、21个碳纤维增强树脂复合材料(CFRP)板-钢板双搭接试件,进行了高温及常温下的准静态拉伸试验、拉伸剪切试验,测试了相应胶黏剂的动态热机械性能,并与常用商品胶的耐热性能与力学性能进行比较,得到以下结论:随混掺固化剂中聚醚胺D230比重的增加,胶黏剂高温下的拉伸强度及弹性模量逐渐降低,断裂伸长率及应变能先增加后减小,缩胺105与聚醚胺D230两种固化剂混掺的推荐比例为1∶2。随固化温度的升高,具有固化剂混掺较佳比例的胶黏剂的玻璃转变温度有所提升,综合技术与经济因素,推荐(较佳)固化条件为90℃、2 h。推荐比例与推荐固化条件的纳米SiO₂环氧胶黏剂在环境温度20~70℃之间的拉伸强度及韧性均大大优于常用商品胶黏剂。基于推荐比例与推荐固化工艺的纳米SiO₂胶黏剂粘结的CFRP板-钢板搭接接头,在70℃服役温度下的荷载-位移曲线存在屈服段,承载能力(较采用单一缩胺105和单一聚醚胺D230固化剂的搭接试件分别提升了104.03%、64.43%)和延性(为采用单一缩胺105固化剂的搭接试件的2.5倍以上)均大幅提升。高温和常温下的黏结-滑移本构均为三线性四边形。胶黏剂在满足耐热性的同时,需尽可能提升其韧性,才能有效提升CFRP-钢搭接界面的力学性能。相比于常用商品胶黏剂,研制的推荐胶黏剂粘结的CFRP板-钢板搭接接头具有优越得多的承载能力和界面断裂能。      

Influence of the properties of externally bonded CFRP on the shear behavior of concrete/composite adhesive joints

This paper concerns the strengthening of concrete structures with externally bonded composite reinforcement, and focuses mainly on the influence of the FRP characteristics on the mechanical behavior of the composite to concrete interface. An experimental investigation was conducted, based on the characterization of such bonded assemblies and using a double lap joint shear test. Twelve different series of specimens were studied in order to evaluate the influence of various parameters related to the FRP material (i.e. the use of carbon or aramid and of fiber reinforced systems, the type of manufacturing process, the values of the Young modulus, the thickness of the FRP and the bonded length) as well as several parameters related to the adhesive joint (i.e. the lap joint thickness, the curing conditions and the elastic modulus of the epoxy adhesive). Analyses of the strain and shear stress distributions along the lap joints emphasized significant effects of the FRP properties and epoxy curing conditions on the interfacial strength. In addition, a bond strength model is proposed in the last part of the study.     

Bond strength of PCC pavement repairs using metakaolin-based geopolymer mortar

In order to use geopolymer mortar as a pavement repair material, a splitting test and a slant shear test are performed to characterize the bond strength of the geopolymer and conventional cement mortar interfaces. Effect of curing time, degradation of the cement mortar under different acid conditions on the bond strength of geopolymer with conventional cement mortar, and comparison of the metakaolin geopolymer with other pavement repair materials are analyzed. It was found that curing time affects the interface bond strength greatly. Metakaolin geopolymer reaches 80% of its 28 day strength in 3 days curing, but shows low strength in 24 h curing. Curing temperature affects the strength of metakaolin geopolymer, however metakaolin geopolymer cured in ambient temperature and the bond strength of 3 days curing through splitting and slant shear tests reaches 3.63 MPa and 16.32 MPa, respectively. Degradation of cement mortar negatively affects the bond strength of geopolymer and conventional cement mortar. Possibility of using metakaolin geopolymer as a repair material is discussed by comparison of this experimental result with these of other repair materials.     

超低温用紫外光快速固化丙烯酸酯树脂体系的制备及性能

在丙烯酸酯体系中加入填料酚酞基聚芳醚酮（PEKC）,通过紫外光（UV）固化交联制备出可快速固化且耐超低温（液氮）的PEKC/丙烯酸酯体系,通过考察PEKC/丙烯酸酯体系的凝胶率及固化收缩率,确定了其在UV固化下的交联程度及固化收缩状况;通过动态热机械分析表征了PEKC/丙烯酸酯体系的线性热膨胀系数（α）,研究了其在温度变化下的尺寸稳定性;测试并比较了PEKC/丙烯酸酯体系在超低温及室温下的剪切强度,表征了其耐超低温性能。结果表明,PEKC与丙烯酸酯质量比为0~4%的PEKC/丙烯酸酯体系可以实现快速固化,固化5 s后树脂的凝胶率可达80%以上。随着PEKC/丙烯酸酯中PEKC质量比从0增加到4%,固化后PEKC/丙烯酸酯体系在-150~50℃温度范围的线性热膨胀系数由6.71×10^-5℃^-1降低至5.29×10^-5℃^-1,体收缩率由25.61%降低至6.24%,线收缩率由1.78%降低至0.41%,而其断裂延伸率逐渐提高,韧性增强。研究发现,PEKC/丙烯酸酯复配体系的室温拉伸强度都在20 MPa以上,PEKC与丙烯酸酯质量比为3%的PEKC/丙烯酸酯体系铝-玻璃搭接在室温和液氮温度下的拉伸剪切强度分别可达17.48 MPa和17.23 MPa。     

Analysis of a modified microbond test for the measurement of interfacial shear strength of an aqueous-based adhesive and a polyamide fibre

The microbond test was used to measure the interfacial shear strength (IFSS) between a polyamide fibre and a water-based polyurethane. Due to the low viscosity of the water based polyurethane, the droplet could not be formed using a conventional preparation method. A disc shaped microbond droplet forms when an aqueous-based colloidal polymer adhesive was deposited onto the pin hole in a mounting card with a vertical polyamide fibre in the middle after drying and curing at an elevated temperature. Since the droplets were formed with a disc shape, which differs from the conventional ellipsoid, a finite element analysis of the stress distribution at the interface for these contrastingly shaped droplets were calculated and compared. The stress analysis showed that the interfacial shear stress profiles were well matched for both providing confidence that the disc-shaped droplets could be used for interfacial analysis. The microbond test using a disc-shaped droplet was used to study the influences of silane treatment and plasma treatment on the interfacial shear strength between a polyamide fibre and an aqueous deposited polyurethane. The interfacial shear strength of the fibre after plasma treatment was 10.3 MPa, much higher than that of the control and the silanised fibres, 5.2 MPa and 5.4 MPa respectively. The results showed that the microbond test could be used to investigate the interfacial properties of the polyamide fibre and water-based polymer adhesive.     

淀粉/酚醛预聚物共缩聚胶黏剂的制备

以玉米淀粉为原料,采用次氯酸钠进行氧化改性,并以聚乙烯醇为接枝剂进行接枝改性,再与酚醛预聚物进行共缩聚反应,制得淀粉/酚醛预聚物(S/PFO)共缩聚胶黏剂。讨论了淀粉/酚醛预聚物比例、共缩聚温度和共缩聚时间对S/PFO共缩聚胶黏剂固体含量、黏度、固化时间、干状胶合强度和湿状胶合强度的影响。结果表明,淀粉/酚醛预聚物比例为15/120,共缩聚温度为90℃,共缩聚时间为2.0 h时,所制得的S/PFO共缩聚胶黏剂综合性能最佳。采用同步热分析和扫描电子显微镜对S/PFO共缩聚胶黏剂的固化性能和胶合界面进行了表征。相比于酚醛树脂胶黏剂,S/PFO共缩聚胶黏剂固化温度和固化焓值均降低,能够有效降低生产能耗。S/PFO共缩聚胶黏剂能将木材表面的孔隙均匀填满,形成一层薄薄的且连续的胶膜,有利于提高其胶接强度和耐水性能。     

低温快速固化环氧导电胶的制备与性能

采用E-51型环氧树脂为导电胶基体树脂, 低分子量聚酰胺树脂(PA)为固化剂, 填加经硅烷偶联剂(KH550)改性后的纳米级和微米级铜粉及助剂制备导电胶。首次采用了液态固化剂(低分子量的聚酰胺酯), 以解决导电胶制备过程中填料用量受限的难题。通过正交试验方法探讨了导电胶中导电填料的含量、导电填料配比、硅烷偶联剂用量和还原剂添加量对导电胶粘接性能和导电性能的影响, 对导电胶的制备工艺进行了优化, 获得了制备导电胶的最佳方案。测试结果表明该导电胶能够在60 ℃下4 h内快速固化。在填料质量分数为65%时, 导电胶具有最低的体积电阻率3.6×10-4 Ω·cm; 导电胶的抗剪切强度达到17.6 MPa。在温度为85 ℃、湿度(RH)为85%的环境下经过1000 h老化测试后导电胶电阻率的变化和剪切强度的变化均不超过10%。      

SY-H2中温固化糊状胶粘剂性能研究

SY-H2为中温固化的单组分糊状胶粘剂，对该胶粘剂的剪切强度、剥离强度、耐水性能、耐老化、耐低温、疲劳和蠕变等综合性能做了详细介绍。     

A Phenol-Amine Superglue Inspired by Insect Sclerotization Process

Exoskeletons of insects formed by sclerotization processes exhibit superstrong properties in moduli. Here, it is demonstrated that mimicking the sclerotization process using phenol and polyamine molecules unexpectedly results in a 100% ecofriendly, biocompatible waterborne superglue. Oxygen presented in air and dissolved in water acts as an initiator producing phenolic radical/quinone for superglue curing. Despite synthesis-free uses of water, phenol, and polyamine, its adhesion strength is comparable to commercial epoxy glue showing >6 MPa in lap shear strength. The phenol-amine superglue bonds to various substrates including ceramics, woods, fabrics, plastics, metals, and importantly biological tissues. Due to strong adhesion, the superglue effectively seals wounds within a few seconds, and, due to its waterborne nature, no harmful respiratory effect is observed because of any release of volatile organic compounds. The easy, cost-effective preparation of the phenol-amine superglue can revolutionize varieties of industrial, biomedical, daily life processes.     

纳米SiO2质量分数对胶粘碳纤维增强树脂复合材料板-钢搭接界面黏结性能的影响

胶黏剂力学性能对碳纤维增强树脂复合材料(CFRP)加固钢结构的界面黏结性能影响显著。基于研制的胶黏剂配比,分析了不同纳米SiO₂质量分数对胶黏剂常温固化后基本力学性能及微观结构的影响,制作了31个CFRP板-钢板双搭接试件,对其进行了常温固化后的承载能力、有效黏结长度、传力模式、黏结-滑移本构等试验研究,得出了纳米SiO₂质量分数对CFRP板-钢板搭接试件界面黏结性能的影响规律,并与常用商品胶黏剂进行了比较。研究结果表明:随纳米SiO₂质量分数的增加,胶黏剂应力-应变关系由线性转变为非线性,应变能、断裂伸长率及剪切强度分别最高提升了292.10%、202.88%和133.12%。微观结构分析表明纳米SiO₂的添加使断面粗糙度显著增加,形成了密集的塑性空穴,产生了更多的微裂纹,使胶黏剂的韧性大幅度提高。当纳米SiO₂质量分数从0增至1wt%,搭接试件破坏模式由界面破坏逐渐变为CFRP板层离破坏。掺入纳米SiO₂能显著增加搭接试件的极限承载力(提升256.96%)及界面有效黏结长度(提升3倍),提高CFRP表面的应变及界面剪应力峰值。纳米SiO₂质量分数为0与0.5wt%的搭接试件的黏结-滑移曲线为双线性三角形模型,纳米SiO₂质量分数为1wt%的搭接试件的黏结-滑移曲线为三线性梯形模型,黏结界面韧性大幅提升。CFRP-钢界面承载能力受胶黏剂拉伸强度与断裂伸长率的双重影响,非线性高强度(即具有较高应变能)胶黏剂对应的CFRP-钢搭接接头具有更好的界面性能。