Use of Dynamic Mechanical Measurements to determine the aging behavior of solid propellant

A process for determining the aging characteristics of solid rocket propellants by measuring their dynamic mechanical properties is described. Samples of rocket propellant are tested using a mechanical spectrometer at low strain levels and low frequencies. The change in the dynamic storage modulus of the propellant with aging time and temperature is used to determine the aging rate anf the likely mechanisms occuring during aging. The technique is advantageous is several respects:

• (1) because the tests are non-destructive and use small test specimens, and entire aging program can be conducted using much less propellant than is required ihn traditional aging programs (propellant requirements are reduced by more than an order of magnitude)
• (2) the technique can be applied to samples with unusual or unique geometries which cannot be tested using traditional methods;
• (3) test specimens can be obtained directly from live, operational solid rocket motors, and service life and mechanical property degradation can be determined.

     

Dynamic mechanical study on the thermal aging of a hydroxyl‐terminated polybutadiene‐based energetic composite

In an attempt to determine the aging behavior of hydroxyl‐terminated polybutadiene‐based composite solid propellants, viscoelastic measurements were used to study the effect of thermal aging on this kind of energetic material. Accelerated‐aging tests at 40, 60, and 80°C were performed for 5000 h. The changes in the dynamic mechanical properties, including the storage modulus (E′) and loss factor or damping efficiency (tan δ), with time and temperature were measured to determine the aging rate and likely mechanisms occurring during this process. An Arrhenius analysis based on the determination of relative rate constants showed a linear tendency from tan δ values, whereas a significant curvature was found from E′ values. In addition, the effects of external (surface) and internal (core) sampling in the intensification of the aging process were analyzed. The results confirmed dynamic mechanical analysis as a powerful tool for determining the aging characteristics of composite propellants. This technique allows the evaluation of the actual state of a propellant grain with a small sample and a straightforward measurement. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2397–2405, 2003     

盐雾老化对风电叶片用环氧树脂性能的影响

采用差示扫描量热(Differential Scanning Calorimetry,简称DSC)、红外光谱(Fourier transform infrared spectroscopy,简称FTIR)、静态力学性能测试等分析方法对复合材料风电叶片用环氧树脂浇铸体老化前后的性能进行分析,通过对比盐雾老化前后树脂浇铸体的玻璃化转变温度(Glass transition temperature,简称Tg)和力学性能,研究了环氧树脂浇铸体的老化机理。结果表明,树脂浇铸体的Tg随着老化时间的增加呈现先上升后下降的趋势,老化20天时Tg由未老化前的55℃升高到62℃,20天后开始下降,到50天时下降为51℃,比未老化的下降了4℃。随着老化时间的增加,树脂浇铸体力学强度和模量均呈下降趋势,50天盐雾老化后树脂浇铸体的弯曲强度和拉伸强度分别下降了13%和12%,而弹性模量和弯曲模量分别下降了16%和9%。     

Isothermal physical aging of a fully cured epoxy—amine thermosetting system

The rate and effects of isothermal physical aging of a fully cured epoxy—amine/glass fiber composite specimen were studied for a wide range of isothermal aging temperatures (−180 to 200°C) using a freely oscillating torsion pendulum technique: torsional braid analysis (TBA). As assigned from the maxima in the mechanical loss vs. temperature, the glass transition temperature, T_g, was 182°C (0.9 Hz), and the principal glassy-state secondary transition temperature, T_β, was ≈ −30°C (1.9 Hz). Plots of the increase in the isothermal modulus and of the decrease in the isothermal mechanical loss were linear vs. log aging time; their slopes provided aging rates. It was found that the isothermal aging rate varies with isothermal aging temperature (T_a) and that there are two maxima in the aging rate vs. T_a. A correlation presumably exists between the two maxima in the aging rate and the two transitions. This is not surprising since mechanical loss maxima (i.e., transitions) and aging rate maxima both correspond to specific, localized, and restricted submolecular motions. Effects after isothermal physical aging were investigated vs. temperature in terms of change of modulus of the specimen. The effect of isothermal aging existed primarily in a narrow temperature region localized about T_a. The majority of the isothermal aging effect can be eliminated by heating to temperatures above T_a, but below T_g. Theoretical and practical implications of this observation are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 55–67, 1997     

H01双基推进剂老化的动态力学性能表征

用动态热机械分析仪测定了65℃下双基固体推进剂H01的老化性能。在低温段（-10～40℃）,随老化时间的增加tanδ值有明显下降,β松弛峰也越来越明显。H01的α松弛的损耗角正切tanδ的峰温、动态柔量J＇和J＂的值以及动态模量E＇和E＂、动态柔量J＇和J＂主曲线的叠合垂直位移因子与老化时间存在一定规律。TG-DTG试验表明,随着老化时间的增加,试样在183℃时的质量损失逐渐减小,说明增塑剂含量随老化时间增加而减小。因此,除了因结构松弛造成的“物理老化”外,这是造成上述各力学损耗量随老化时间下降的又一主要原因。     

Aspects of physical aging,mechanical rejuvenation,and thermal annealing in a new copolyester

Long‐term effects of physical aging and mechanical rejuvenation are monitored through dynamic mechanical properties of an amorphous glassy polymer. These phenomena are investigated through dynamic mechanical testing that evaluates in situ the evolution of the storage modulus with time during annealing and physical aging. Comparisons are made on samples with different thermal histories and mechanical treatment (rejuvenation). The polymer characterized in this contribution is a new commercially available copolyester under the tradename of Tritan?. The results are discussed in context to different aging rates obtained from the various thermal and mechanical treatments; both measurements of aging rates are compared. POLYM. ENG. SCI., 55:1941–1950, 2015. © 2014 Society of Plastics Engineers     

Probing the Damping Property of Three-Dimensional Graphene Aerogels in Carboxylated Nitrile Butadiene Rubber/Polyurethane Blend

Three-dimensional (3D) graphene aerogel (GA) with a spatial porous structure and network skeleton was facilely prepared via one-step self-assembly hydrothermal reduction. Such network structure is regarded as a critical advantage in resolving the dispersion of graphene in polymer matrix, thereby enhancing the damping property. Here, as-prepared GA was added to the carboxylated butadiene nitrile rubber/polyurethane blend (XNBR/PU) by melting/mechanical complex method. Their dynamic mechanical properties were investigated in detail, and the relationship between thermal aging and dynamic mechanical properties had also been studied. Finding that the storage modulus and loss modulus of XNBR/PU were continually improved with the increase in addition amount of high-performance GA, reaching 3,219 and 316 MPa with the content of 3 wt% GA, respectively. Loss factor (tanδ) of XNBR/PU with GA shows two sets of maximum values (0.22 and 0.61) at around −25 and 0.6°C, respectively. Results illustrate that GA can greatly improve the damping performance, damping temperature range, mechanical properties, and thermal aging resistance of XNBR/PU blend, mainly depending on the performance characteristics of GA and interface interaction between GA and XNBR/PU. Verifying that GA with 3D network structure holds a great prospect for damping materials. POLYM. ENG. SCI., 60:61–70, 2020. © 2019 Society of Plastics Engineers     

阻燃型玻纤增强PA10T复合材料的热氧老化性能

采用溴化环氧树脂对聚对苯二甲酰葵二胺(PA10T)进行改性,并通过熔融共混法制备阻燃型玻璃纤维(GF)增强PA10T复合材料,采用人工加速热氧老化手段,研究了热氧老化对其力学性能的影响,并用扫描电子显微镜(SEM)对复合材料的冲击断面形貌进行观察。结果表明,随热氧老化时间增加,复合材料的拉伸强度、弯曲强度和缺口冲击强度均下降明显,分子链松弛过程减弱;老化10 d后,复合材料的弯曲弹性模量仅略有下降而储能模量达到最大值,表明在热氧老化初期PA10T分子链之间发生了微交联,但随老化时间继续增加,两者均下降明显。SEM结果表明GF与树脂基体之间界面粘接作用的强弱是影响材料热氧老化性能变化的主要因素。     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

丁羟推进剂/衬层界面黏结性能劣化的动态力学表征

研究了高温加速老化过程中丁羟推进剂联合黏结试件的老化特性,探索了利用动态力学表征丁羟推进剂/衬层界面(P/L界面)黏结性能劣化的方法.结果表明,高温老化使黏结件P/L界面黏结强度增大,推进剂中可迁移组分向衬层的迁移量增加,衬层降解,这使得P/L界面两侧材料力学性能差异增大,缺陷增多,P/L界面黏结性能劣化.动态力学分析实验表明,衬层初始模量、界面推进剂和本体推进剂的储能模量与黏结件黏结强度具有相关性,可作为表征P/L界面黏结性能劣化的参数.给出了利用动态力学参量表征黏结件黏结强度的回归关系.     

Mechanical properties and thermal aging behavior of styrene‐butadiene rubbers vulcanized using liquid diene polymers as the plasticizer

The mechanical properties of styrene‐butadiene rubber (SBR) vulcanizates prepared using various plasticizers including liquid polybutadiene and styrene‐butadiene copolymers were investigated. The effect of the liquid polymers as the plasticizers on the mechanical properties of the polymers, such as the hardness, tensile storage modulus, tanδ, and the modulus at 100% elongation values, were determined before and after the thermal aging. As a result, it was revealed that the use of these liquid polymers gave less amount of change in the measurement values for the mechanical properties during the aging. The crosslinking density and the amount of free polymers were also determined on the basis of the swelling and extraction data, respectively, using several organic solvents. These results support the fact that the added liquid polymers are fixed to the SBR networks. We revealed the superiority of the liquid styrene‐butadiene copolymers as the plasticizer, which provides sufficient mechanical properties after vulcanization and the excellent maintenance of the properties during the thermal aging process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Young’s modulus measurements of magnesia–spinel composites using load–deflection curves, sonic modulus, strain gauges and Rayleigh waves

The extent of interlinking of the microcracking and a decrease in strength and modulus values were determined to be a function of both spinel particle size and volume fraction to allow calculation of thermal shock parameter, R. Measurements of Young’s modulus were carried out both at room temperature and after thermal shock testing by using the load–deflection curves (defined as “mechanical” modulus) and by the sonic modulus technique. The values obtained from these methods were significantly different for quenched/unquenched samples. To understand the basis for these differences, strain gauge and Rayleigh wave methods were also used to determine Young’s modulus of the composites. Modulus values obtained from these methods confirmed the differences measured, and provided a guide to the values to be used in calculating thermal shock parameters. The mechanical modulus technique was considered the most meaningful indicator of Young’s modulus for a situation in which large mechanical strains were to be applied to the materials during thermal shock.     

加速紫外老化对聚乙烯薄膜力学性能的影响

介绍了聚乙烯(PE)薄膜老化机理,并对PE薄膜进行了人工加速紫外光老化试验。分析了老化时间对PE薄膜力学性能的影响。结果表明:紫外光的照射使PE的化学键发生交联和断裂反应,其中断裂反应占主导,使聚合物分子量减小,物理性能下降;PE薄膜的拉伸强度、断裂伸长率和弹性模量随老化时间的延长而降低;PE薄膜抵抗破坏的能力在老化60 h以上会急剧下降,而此时弹性模量的变化趋势变得平缓,断裂伸长率与老化时间近似成线性关系递减。     

缓冷玻璃态PVC在拉伸应变状态下的老化特性

用万能拉力机、差示扫描量热仪和动态黏弹仪测试了聚氯乙烯拉伸应变的老化特性.并与物理老化进行比较.在相同老化时间内,应变老化试样的屈服应力和弹性模量高于物理老化试样,而断裂伸长率却小于物理老化试样:应变老化试样的吸热峰面积和储存弹性模量大于物理老化试样.     

剑麻纤维/聚丙烯木塑复合材料的热氧老化性能研究

以剑麻纤维(SF)、聚丙烯(PP)为原料,经熔融共混、模压成型工艺制备木塑复合材料。探讨了SF/PP复合材料的力学性能、热性能随老化时间和SF含量的变化规律,借助扫描电镜对复合材料老化前后的冲击断面进行微观结构分析。结果表明:老化后复合材料的冲击强度、弯曲强度和弯曲模量随剑麻含量的增加而降低;同时,复合材料中PP相的结晶速率、结晶度也有所降低,但复合材料的热稳定性基本没有变化。     

苯乙烯-丁二烯-苯乙烯嵌段共聚物改性沥青的老化性能

考察了苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)和加入含硫稳定剂的SBS改性沥青老化后的动态力学性能、黏度变化和低温物理性能。结果表明,SBS与含硫稳定剂的加入改善了老化后沥青的高温性能;老化后的改性沥青表现出更好的高温刚性,蠕变劲度降低,蠕变速率增大,老化后沥青的低温性能提高,且长期使用性能良好。     

缓冷玻璃态ABS在拉伸应变状态下的老化行为

用万能拉伸实验机和差示扫描量热仪(DSC)对物理老化和应变老化的ABS试样进行研究。力学性能测试结果表明:在相同老化时间内,应变老化试样的屈服应力和弹性模量高于物理老化试样,而断裂伸长率却小于物理老化试样。DSC测试表明:在相同老化时间内,应变老化试样比物理老化试样的热流吸收峰面积更大,说明应变老化试样形成了与物理老化试样不同的结构。     

浇注PBX炸药老化过程中交联密度与力学性能的关系

为分析浇注PBX炸药交联密度与力学性能的关系,在70℃时对浇注PBX炸药样品进行高温加速老化试验,对比分析了平衡溶胀法和核磁共振(NMR)法测定交联密度的差异,研究了其在常温时的抗拉强度(σm)、抗压强度(σb)、压缩率(εb)、抗剪强度(τ)、硬度(SH)与黏结剂母体凝胶分数(G)、交联密度(ve)之间的关系。用动态热机械分析仪(DMA)分析了不同老化时间下样品损耗因子tanδ和黏弹系数的变化规律。结果表明,PBX炸药样品的交联密度在老化初期增加,老化中期略有降低,老化后期又增加;NMR法因其测试简单、快捷,精确度高、试样非破坏性等优点,可以作为今后浇注PBX炸药交联密度表征方法的一个重要发展方向;样品老化过程中,浇注PBX炸药样品的交联密度与各力学性能的变化呈线性相关,其力学损耗降低的原因是黏结剂母体的G和v_e增加,浇注PBX炸药的降解和交联是由黏结剂母体结构变化引起。     

Moisture durability of four moisture cure urethane adhesives

Moisture durability of four low modulus adhesives was examined. The four low modulus adhesives all had the same basic moisture cure polymer but contained different fillers and additives. Hot-dipped galvanized steel was bonded to random fiber-reinforced unsaturated polyester and aged in two moisture environments for various durations. Adherend surface wipes included acetone, isopropyl alcohol and a typical surface contamination for galvanized steel (an organic lubricant). Diffusion coefficients, moisture uptake and modulus changes due to moisture environment were determined for the adhesives and the fiber-reinforced plastic (FRP). The moisture cure adhesive with clay and poly(vinyl chloride) (PVC) as fillers (adhesive 252) had the highest retained lap joint strengths. Initially, adhesive 252 had single lap joint strengths of 1.47 ± 0.08 MPa for acetone-wiped joints and 1.39 ± 0.33 MPa for organic lubricant-wiped joints. After accelerated aging in a cataplasma environment for 9 weeks, lap joint strengths fell to 0.61 ± 0.08 MPa for acetone-wiped joints and to 0.65 ± 0.11 MPa for organic lubricant-wiped joints. Environmental scanning electron microscopy (ESEM) and energy-dispersive spectrometry (EDS) showed that the actual failure locus was through a corroded zinc layer and between the adhesive and the zinc surface after aging. Dynamic mechanical analysis (DMA) showed that the modulus for adhesive 252 dropped from 21.7 to 13.9 MPa after cataplasma aging. From finite element analysis (FEA), this modulus drop corresponded to a drop in normal stress concentration from 0.75 to 0.57, and a drop in shear stress concentration from 1.41 to 1.36 at a point 0.5 mm from the end of the single lap joint overlap.