Mechanical and scratch behaviors of polyrotaxane-modified poly(methyl methacrylate)

The mechanical and scratch behaviors of polyrotaxane (PR) modified poly(methyl methacrylate) (PMMA) were investigated. PR is a necklace-like supramolecule with rings threaded onto a linear backbone chain that is capped by bulky end groups. Cyclodextrin (CD) serves as the ring structure and can be functionalized to induce specific interactions with the hosting polymer matrix. To systematically investigate the effect of CD functionalization on the mechanical properties of PMMA, PR with polycaprolactone (PCL) grafted chains on CD, and PR with methacrylate functional groups at the terminal of the PCL grafted chains on CD were chosen for this study. Tensile and compressive true stress–strain tests, ASTM scratch test, and coefficient of friction measurements were conducted to fundamentally understand how PR influences the mechanical and scratch behaviors of PMMA. Additionally, dielectric relaxation spectroscopy and dynamic mechanical analysis were conducted to explore how PR influences the relaxation dynamics of PMMA. The above findings suggest that the methacrylate functional group on PR induces favorable molecular interactions with PMMA matrix, leading to enhanced molecular cooperativity during deformation, which in turn improves tensile and compressive properties and achieves greatly improved scratch resistance.     

The effect of physical ageing on the properties of poly(ethylene terephthalate)

Physical ageing rates of poly(ethylene terephthalate) have been measured, and ageing is interpreted to be associated with the conventional glass formation process, which occurs at a more rapid rate at higher temperatures. Ageing is accompanied by a marked change in mechanical properties, increased tensile yield stress and drawing stress, more localized yielding of the polymer and a marked decrease in impact strength. The fracture results have been attributed to the increased yield stress and a change in contribution of plane stress and plane strain conditions in the samples. Fracture surfaces show evidence of mixed modes of fracture.     

Relationship between viscoelasticity and scratch morphology of coating films

In order to make clear the relationship between viscoelasticity of coating film and its scratch resistance, a number of clear coatings were examined by surface observation and measurements of their mechanical properties.

The scratches can be classified into two types by means of optical microscopic observation with attached polarizing filter, scraped fracture-type and plastic deformation-type. The ratios of the damaged areas to the whole observed areas were determined by image analysis as a measure of scratch resistance.

The comparison between the relaxation spectrum of the coatings and the ratio of the scratched area showed that the degree of surface damage caused by a scratch tester which simulated car washing machine correlated with the storage modulus of the coatings G_sr, at a relaxation time of 1 s. Moreover, the degree of plastic deformation by scratches depended also on S_pls, the minimum strain which could cause plastic deformation in the film.     

Effect of long-chain branching molar fraction on scratch behavior of polypropylene

Polymers containing a certain amount of long-chain-branching (LCB) structure are expected to possess improved mechanical properties over those of the linear structure counterpart. However, fundamental knowledge on the structure–property relationship in LCB containing polypropylene (PP) is still illusive. In the present study, a set of model PP systems containing an increasing molar fraction of LCB (5–19 mol%) were prepared by reactive extrusion to determine how LCB content may influence the scratch behavior of PP. It is shown that with only 5 mol% of LCB content in PP can improve resistance against scratch-induced fish-scale formation by over 25%. The improvement of scratch resistance is attributed to the increases in entanglement density in LCB-containing PPs, which is evidenced by their creep-recovery behavior. The present study demonstrates that the incorporation of LCB in PP leads to higher viscoelastic recovery and increased tensile strength, which account for the observed improvement in scratch performance. The usefulness of LCB in polymers for improving scratch performance is discussed.     

Correlation between the wear resistance, and the scratch resistance, for nanocomposite coatings

The nanoscratch test, used in this study, quantitatively characterizes the scratch behaviour of coatings. Some of the obtained parameters are plastic and elastic deformation, critical load to start the scratch, chipping or other change in the scratch mechanism of the coating. The knowledge of the scratch mechanism allows the optimisation of the material behaviour. In the present study the scratch resistance with the wear resistance has been correlated for nanocomposite coatings. Knowledge of mechanical properties extracted from the scratch test, supports the optimization of the coating against wear. The study was applied to nanocomposite coatings with different polymer matrices, different percentages and nature of nanoparticles.     

Analysis of scratch characteristics of automotive clearcoats containing silane modified blocked isocyanates via carwash and nano-scratch tests

The aim of this study was to investigate the scratch characteristics of automotive clearcoats based on an acrylic polyol resin, with butylated melamine and silane modified blocked isocyanates, using car-wash and nano-scratch tests.To scrutinize the effect of silane modified blocked isocyanate on the chemical and mechanical properties of clearcoats, with respect to changes in the crosslinking networks inside the clearcoats due to the curing reaction, dynamic mechanical analysis (DMA) and FT-IR analysis were performed. The scratch behaviors were analyzed via Amtec–Kistler car-wash and nano-scratch tests, accompanied with scratch images simultaneously visualized using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The basic properties of various automotive clearcoats such as impact resistance, pencil hardness, solvent resistance, and stone-chip resistance, were also compared. The results showed that a close correlation existed between the scratch resistance data obtained from the car-wash and nano-scratch tests for clearcoats made from acrylic polyol resin, with melamine and silane modified blocked isocyanates. Also, all the mechanical properties, including scratch resistance, noticeably improved due to the increased crosslinking networks via the formation of urethane bonds, when the portion of silane modified blocked isocyanates was increased. This was verified from the surface profiles and images of the scratched clearcoats captured using AFM and SEM.     

Evolution of mechanical properties of polypropylene separator in liquid electrolytes for lithium‐ion batteries

Knowledge of the mechanical behaviors of polymeric separators immersed in liquid electrolytes is of great significance for predicting the long‐term performance of lithium batteries with high performance and safety. In terms of tensile tests, heating shrinkage, and dynamic mechanical analysis as well as the essential work of fracture method, the study reported here encompasses a systematic investigation of the mechanical properties of a typical commercial polypropylene separator in mixtures of ethylene carbonate and dimethyl carbonate and lithium hexafluorophosphate (LiPF₆), comparing with the results in ionic liquid (IL) electrolyte composed of lithium tetrafluoroborate (LiBF₄) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIBF₄) and dry condition. It has been found that liquid electrolytes have obvious negative effect on the dimensional stability at elevated temperature and mechanical properties, especially on crack resistance of the polymer separator. LiBF₄‐BMIBF₄ has much smaller damage on the strength, Young's modulus and fracture toughness of separator than the organic solution except the dynamic modulus at high temperature. Notably, the maximum tensile stress, Young's modulus and the reciprocal of relaxation time of the polymer separator are linearly dependent with strain rate under quasi‐static condition, and the relaxation time has clarified the coupling effect mechanism of liquid electrolyte and loading rate. Moreover, the non‐dimensional viscoelastic constitute equation could perfectly track the tensile behavior of wet and dry separators at different strain rate, and a property model could well characterize the temperature‐dependent storage modulus of polymer separators from rubbery to viscous state. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46441.     

Surface damage resistance and yielding of chemically strengthened silicate glasses: From normal indentation to scratch loading

We report on surface elasticity, plastic deformation and crack initiation of chemically strengthened soda-lime silicate and sodium aluminosilicate glasses during lateral indentation and scratch testing. Instrumented indentation using a normal indenter set-up corroborated previous findings on the effects of chemical strengthening on surface Young's modulus, hardness, and indentation cracking. Using lateral indentation in the elastic-plastic regime, we find a pronounced increase in the scratch hardness as a result of chemical strengthening, manifest in higher work of deformation required for creating the scratch groove. Thereby, the glass composition is found to play a stronger role than the absolute magnitude of surface compressive stress. Using a blunt conical stylus for instrumented scratch testing reveals three distinct modes of scratch-induced surface fracture, which occur during scratching or after unloading. Occasional micro-cracking caused by pre-existing surface flaws at low scratching load can be completely suppressed through chemical strengthening. The intrinsic defect resistance to microcracking is reduced as a result of ion stuffing, depending on the initial glass composition, whereas the resistance to abrasive yielding is enhanced by several hundred MPa.     

The effect of gamma ray irradiation on the mechanical properties of large cross-section oriented polyethylene rods

The effect of gamma irradiation, in acetylene, on large diameter oriented polyethylene has been investigated. The dependency of gel content, melting point, and crystallinity on dose was evaluated. The gel content dose relationship showed two regions, indicating that an effective network is formed at low doses, 60 kGy. Irradiating the oriented rod in acetylene was found to more than double the initial tensile modulus. This improvement in the tensile properties resulted in improved creep–strain resistance for the material. These improvements in the mechanical properties were attributed to crosslinks formed both in the amorphous regions and at the surfaces of the crystalline regions. At high does > 180 kGy degradation of the oriented polymer resulted in a deterioration in mechanical properties.     

The brittle fracture of amorphous thermoplastic polymers

The brittle fracture properties of polyphenylene oxide, polysulfone, polycarbonate, and poly(methyl methacrylate) thermoplastic polymers were investigated over a wide range of temperatures. Fracture energy measurements were made using double edge-notched tensile samples. Tensile strength, tensile strain, and initial elastic modulus were measured for calculation of the fracture energy and further analysis of the polymer behavior. It was found that mechanical transitions in the tensile properties corresponded reasonably well with transitions in the fracture energy in the temperature range investigated. Fracture surface photographs permitted visual analysis of the fracture process. It was found that the roughest fracture surface corresponded to the maximum in the fracture energy for a given polymer. A theory for prediction of polymer tensile yield strain is presented, based on the volume dilation concept. The implications of this theory are discussed in terms of the crack tip flow process leading to brittle fracture.     

Mechanical behavior of tetrafunctional/phenol novolac epoxy mixtures cured with a diamine

An amine‐cured epoxy system based on tetraglycidyldiaminodiphenylmethane and a novolac glycidyl ether resin was studied. Epoxies were prepared by varying the cure schedules and using the isothermal time–temperature–transformation diagram of the system. The materials were characterized using dynamic‐mechanical analysis (DMA), tensile stress–strain tests over a range of temperatures and testing speeds, impact, and hardness tests. Optical microscopy was used to study the fracture surfaces of the samples. Some interrelations between the behavior and the microstructure of the system are discussed. In addition, the effect of thermal aging on the mechanical properties has been studied. DMA analysis seemed to reveal a structure that tended to be less heterogeneous with increasing the crosslink density. The advance in the etherification reactions or the thermal aging has reduced the mechanical properties related with the consumption of energy to break. The optimal cure schedule according to the global properties has been established. The morphology of fractured surfaces by optical microscopy showed a clear correlation with the variation of the tensile properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2305–2313, 2000     

Study of the structure,properties, scratch resistance and deformation behaviour of graded Cr-CrN-Cr(1-x)AlxN coatings

An in-depth investigation of the structure, properties, scratch adhesion characteristics of graded Cr-CrN-Cr_(1-x)Al_xN coatings synthesized onto M42 steel substrates using closed – field unbalanced magnetron sputtering (CFUBMS) was carried out. Advanced microscopy (scanning and transmission electron microscopy), focused ion beam (FIB) imaging, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and micro–scratch tests was used to investigate the microstructure, mechanical properties and scratch performance as a function of Al content. FIB and TEM investigations revealed that the coatings exhibited a distinct structure; i.e., an adhesive Cr layer, a CrN transition layer and a graded CrAlN top layer with a face centered cubic (FCC) B1 structure. A columnar morphology was exhibited by the coatings and the dimensions of the columnar grains decreased with increasing Al content. Residual stress measurements, obtained from the XRD – sin²ψ method, revealed increasing compressive stresses with increasing Al content. Furthermore, nanoindentation tests showed an increase in mechanical properties, fracture toughness index (H/E) and plastic deformation resistance (H³/E²) as the Al content increased, accompanied by a decrease in the critical load, L_C, during scratch testing implying a decrease in scratch toughness.     

Roles of additives in scratch resistance of high crystallinity polypropylene copolymers

Scratch behavior in neat and talc‐filled high crystallinity polypropylene (PP) copolymers containing various additives is investigated using a cosntant load scratch test and two types of indentation tests (Rockwell and Shore D). The talcfilled PP copolymer exhibits high scratch visibilityand scratch depth. The addition of a nucleating agent or lubricant improves the scratch resistance of the talc‐filled PP copolymer. Differential scanning calorimetry, scanning electron microscopy and attenuated total reflectance Fourier transform infrared spectroscopy are used to characterize crystallinity morphology and scratch mechanisms in PP systems. It is found that the scratch resistance of the PP copolymer systems investigated, in terms of scratch depth and scratch visibility, depends mainly on the fracture features generated during the scratch process. The influences of talc, nucleating agent and lubricant on the scratch behavior of PP are discussed.     

Metrology for characterizing scratch resistance of polymer coatings

Current methods for scratch resistance assessment are often based on “relative but not quantitative” types of measurements, such as visual inspection, gloss changes, and changes in gray scale level or lightness. Most results are used for qualitative assessment purposes, which result in the lack of a repeatable and reliable standardized test method for the polymer materials community. To implement a scientifically based standardized test method for quantifying scratch resistance, it is vital to understand the relationships between material mechanical properties, morphology, and appearance (optical properties) of surface and subsurface deformation. In this article, preliminary results from a scratch testing protocol to identify the “onset” of plastic deformation in poly(methyl methacrylate) and poly(propylene) commercial samples are presented. Recent advances in optical scattering measurements to identify the onset of plastic deformation by analyzing specular and off-specular intensities are also presented. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Mechanical characterization of polymeric films using depth-sensing instrument: Correlation between viscoelastic-plastic properties and scratch resistance

The scratch behavior of polymer films deposited on PMMA substrate by three different coating techniques is investigated by scratch tests using a depth-sensing instrument. Using an improved measurement technique, we develop an advanced methodology based on a more appropriated model that includes an estimation of realistic stress and strain states during scratch tests. The scratch resistance is evaluated by comparing the average contact pressure for which the coating cracks, by taking into account the elastic–plastic behavior of the layer. The proposed model allows the determination of the true contact depth and the elastic recovery at the rear side of the elastic–plastic contact, and thus the true projected contact area between the moving tip and the polymeric surface. This determination depends first on a rheological factor estimated from standard load–displacement curves obtained by nanoindentation and then on the tip geometry. The viscoplacticity index and the activation volume of each type of coating are then determined by nanoscratch. The viscoplasticity index determined during an elastic–plastic contact and the activation volume related to the ductile–brittle transition are discussed as reliable criteria for determining which bilayer system (polymeric film on PMMA substrate) will truly exhibit better wear and scratch resistances in service.     

Investigation of mechanical properties of unidirectional steel fiber/polyester composites: Experiments and micromechanical predictions

The article introduces steel fiber reinforced polymer composites, which is considered new for composite product developments. These composites consist of steel fibers or filaments of 0.21 mm diameter embedded in a polyester resin. The goal of this investigation is to characterize the mechanical performance of steel fiber reinforced polyester composites at room temperature. The mechanical properties of unidirectional steel fiber reinforced polyester composites (SFRP) are evaluated experimentally and compared with the predicted values by micro‐mechanical models. These predictions help to understand the role of material and process parameters on material properties. Two types of SFRP were studied: polyester resin reinforced by both steel fabric containing unidirectional fibers and steel fibers wound on a metal frame with 0° orientations. The effects of the fiber volume fraction and the role of polymer yarns (weft) on mechanical properties were analyzed through tensile, compressive, and shear tests. These tests were performed as per the standard test procedures. In particular, issues related to processing difficulties, polymer yarns effect on properties, standardized testing, and properties under various loading conditions were addressed. Microscopic observations were analyzed to assess the laminate quality and the macroscopic fracture surfaces of shear test specimens were studied by standard techniques. POLYM. COMPOS., 37:627–644, 2016. © 2014 Society of Plastics Engineers     

Multiple scratch tests and surface-related fatigue properties of monolithic ceramics and soda lime glass

In this study, the scratch resistance of several monolithic structural ceramics and soda lime glass was investigated using repeated scratching. Rockwell indentation was used to perform unidirectional multi-pass scratches at progressive loads. It is shown that there is a build up of sample damage as the number of scratches increases, the severity of which being assessed by measuring the depth of the scratches and by performing optical observations of the worn tracks. For each applied load, there is a critical number of passes above which the material removal rate increases dramatically through chipping. By plotting the critical number of passes against the applied load, strength/number of cycles (S/N) like diagrams can be obtained. Although soda lime glass exhibits a lower resistance than most of ceramics for single scratch tests, the glass removal rate becomes similar to that of ceramics when repeated scratch tests are considered. It is suggested that the material resistance to multiple scratch tests rely on the presence of a thin layer of re-compacted and plastically deformed material under the action of the indenter. The absence of such a layer in silicon carbide may explain the surprisingly poor resistance of this material for high applied forces and important number of cycles. It is suggested that this layer improves the material resistance against scratching by decreasing the friction coefficient, thereby diminishing the level of stresses generated within the specimen.     

熔融沉积工艺参数对热塑性聚氨酯弹性体静动态力学性能的影响

为揭示通过熔融沉积成型（FDM）工艺制备的热塑性聚氨酯弹性体（TPU）的静动态力学性能及工艺参数对其力学性能的影响,采用万能材料试验机和分离式霍普金森压杆（SHPB）实验装置对使用3种打印速率（10、40、70 mm/s）和3种喷头温度（200、220、240 ℃）制备的TPU开展准静态（0.01 s^-1）和动态（1 000 s^-1）加载下的力学性能试验,并进行工艺参数优选,同时进一步获取了材料在较宽应变率范围（0.001~2 500 s^-1）的应力?应变样本空间数据。结果表明,准静态和动态加载下,喷头温度220 ℃、打印速率40 mm/s为最优工艺参数;试样在准静态和动态下均具有应变率效应;准静态下试样超弹性特征显著,动态下结合朱?王?唐（ZWT）方程构建的材料黏弹性本构模型拟合曲线与实验曲线吻合较好;采用最优工艺参数制备的试样出现明显“微相分离”现象。     

Tensile properties of Argiope trifasciata drag line silk obtained from the spider's web

The tensile properties of Argiope trifasciata (Argiopidae) drag line silk retrieved from mooring threads in the web were characterized. Scanning electron microscope images were used to determine the cross‐sectional area of the samples, allowing force‐displacement plots to be rescaled as stress–strain curves and to characterize fracture surfaces. Twenty‐eight samples were tested to obtain statistically significant values of the mechanical parameters (elastic modulus, stress and strain at the proportional limit, and tensile strength). The tensile strength of the material was subjected to a Weibull analysis—the first time that this has been attempted with a spider silk. A low value of the Weibull modulus, m = 3.4, was obtained, demonstrating that drag line monofilament does not have a sufficiently reliable tensile strength to function as an engineering material on its own. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2245–2251, 2001     

Influence of scratch load and speed in scratch tests of bilayer powder coatings

The knowledge of the properties of the coatings in terms of scratch and wear resistance is of paramount importance in order to prevent the formation of severe damages. Nonetheless, dealing with the evaluation scratch or wear resistance of an organic coating can be troublesome. They can be strongly dependent on the status of the organic material as well as on the contact condition, applied load and strain rate. Besides, reliable responses cannot be achieved if an appropriate experimental design and a combined usage of proper equipments is not scheduled. In this respect, the present analysis deals with the application of variable speed and load scratch tests to characterize the scratch response and wear resistance of bilayer metal flakes powder coatings. Experimental findings allowed the achievement of consistent trends of the deformation response vs. curing temperature, scratch load and speed as well as their empirical modelling. This way, the overall scratch resistance of the bilayer coatings could be usefully predicted on a broad range of operational conditions, thus providing helpful indications to paint manufacturers and coaters on how to best deal with the application of metal flake powders.