Measuring the Surface and Bulk Modulus of Polished Polymers with AFM and Nanoindentation

Abstract

A new method to determine the elastic modulus of a material using the atomic force microscope (AFM) was proposed by Tang et al. [Nanotechnology 19, 495713 (2008)] and is used in this study. This method models the cantilever and the sample as two springs in a series. The properties of both the spring and cantilever are determined on two reference samples with known mechanical properties and these properties are then used to find the elastic modulus of an unknown sample. The indentation depth achieved with AFM is in the nanometer range (30–130 nm in this study); and hence when this technique is performed on polymers, whose surface structure is different from their bulk structure, AFM gives a measure of the surface elastic modulus. In the present study, after employing AFM to measure the surface modulus of five polymers, traditional depth-sensing nanoindentation, with penetration depths of about 1 μm, was used to determine the elastic modulus in the bulk. The mean values for elastic modulus from the AFM were within 5–50% of the nanoindentation results, suggesting the existence of a surface modulus for polished polymers.     

改性纳米TiO_2对纸张涂料及涂布纸性能的影响

研究了改性纳米TiO2对纸张涂料流变行为和涂布纸性能的影响。研究发现,在同一剪切速率下,随着改性纳米TiO2用量的增加,纸张涂料的表观黏度逐渐增大,且含改性纳米TiO2的纸张涂料具有较高的弹性模量和黏性模量,相位角则较低;随着改性纳米TiO2的用量在0~10%范围内增加,涂布纸的光学性能和印刷适性持续改善,且涂层表面结构的SEM和AFM观察显示,含改性纳米TiO2的纸张涂层表面具有较优的微观孔隙结构。     

Biaxial elastic modulus of very thin diamond-like carbon (DLC) films

The biaxial elastic modulus of very thin diamond-like carbon (DLC) films was measured by the recently suggested free overhang method. The DLC films of thickness ranging from 33 to 1100 nm were deposited on Si wafers by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) or by the filtered vacuum arc (FVA) process. Because the substrate was partially removed to obtain sinusoidal free overhang of the DLC film, this method has an advantage over other methods in that the measured value is not affected by the mechanical properties of the substrate. This advantage is more significant for a very thin film deposited on a substrate with a large difference in mechanical properties. The measured biaxial elastic moduli were reasonable values as can be judged from the plane strain modulus of thick films measured by nanoindentation. The biaxial elastic modulus of the film deposited by r.f.-PACVD was 90±3 GPa and that of the film deposited by FVA process was 600±50 GPa. While the biaxial elastic modulus of the film deposited by FVA is independent of the film thickness, the film deposited by r.f.-PACVD exhibited decreased elastic modulus with decreasing film thickness when the film is thinner than 500 nm. Although the reason for the different behavior could not be clarified at the present state, differences in structural evolution during the initial stage of film growth seem to be the reason.     

Microstructure and mechanical properties of Mo/DLC nanocomposite films

Mo-doped diamond-like carbon (Mo/DLC) films were deposited on stainless steel and Si wafer substrates via unbalanced magnetron sputtering of molybdenum combined with inductively coupled radio frequency (RF) plasma chemical vapor deposition of CH₄/Ar. The effects of Mo doping and sputtering current on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, atomic force microscopy (AFM), and nano-indentation. It was found that Mo doping led to increase in the content of sp² carbon, and hence decreased the hardness and elastic modulus of Mo/DLC films as compared with that of DLC films. The content of Mo in the films increased with the increasing sputtering current, and most of Mo reacted with C atoms to form MoC nanocrystallites at a higher sputtering current. Moreover, the Mo-doped DLC films had greatly decreased internal stress and increased adhesion to the substrate than the DLC film, which could be closely related to the unique nanocomposite structure of the Mo-doped films. Namely, the Mo/DLC film was composed of MoC nanoparticles embedded in the cross-linked amorphous carbon matrix, and such a kind of nanostructure was beneficial to retaining the loss of hardness and elastic modulus.     

Characterization of Films with Thickness Less than 10 nm by Sensitivity-Enhanced Atomic Force Acoustic Microscopy

We present a method for characterizing ultrathin films using sensitivity-enhanced atomic force acoustic microscopy, where a concentrated-mass cantilever having a flat tip was used as a sensitive oscillator. Evaluation was aimed at 6-nm-thick and 10-nm-thick diamond-like carbon (DLC) films deposited, using different methods, on a hard disk for the effective Young's modulus defined as E/(1 - ν ²), where E is the Young's modulus, and ν is the Poisson's ratio. The resonant frequency of the cantilever was affected not only by the film's elasticity but also by the substrate even at an indentation depth of about 0.6 nm. The substrate effect was removed by employing a theoretical formula on the indentation of a layered half-space, together with a hard disk without DLC coating. The moduli of the 6-nm-thick and 10-nm-thick DLC films were 392 and 345 GPa, respectively. The error analysis showed the standard deviation less than 5% in the moduli.     

承压条件下声子晶体吸声性能研究

声子晶体是一种新的吸声材料,研究了局域共振单元包覆层模量、厚度以及橡胶基体模量对声子晶体共振吸声频率、吸声系数的影响规律。在常压及承压条件下,包覆层模量越高,厚度越小,共振吸声频率越高,其规律符合共振频率与包覆层模量、厚度之间的关系。随着压力的增加,声子晶体的共振吸声频率均向高频移动。承压条件下,包覆层模量较低的样品低频吸声系数略高。包覆层厚度为2mm的样品,常压及承压条件下低频吸声系数数值变化较小。基体橡胶模量对声子晶体吸声频率和吸声系数未见明显影响。     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

A study of microstructural and electrochemical properties of ultra-thin DLC coatings on altic substrates deposited using the ion beam technique

Microstructural and electrochemical characterization of diamond like carbon (DLC) ion beam-deposited on AlTiC (70 wt% Al₂O₃+30 wt% TiC) substrate has been carried out. Tapping mode atomic force microscopy (AFM) imaging showed that the island-like topography of DLC-coated substrates is similar to the un-coated one, indicating the uniform coverage of DLC without visible pinholes. Confocal micro-Raman analysis demonstrated that the total Raman intensity, as well as the I_D/I_G ratio, increases with the coating thickness. Electrochemical impedance spectra showed that with the increasing DLC coating thickness, a transition from one-time constant response to two-time constant response occurred when the coating thickness equals 5 nm (IS2), indicating the existence of micro-defects in the coatings which are invisible for AFM. More detailed analysis using the equivalent circuit model revealed that the charge transfer resistance (R_ct) at electrolyte/substrate interface and the resistance (R_p) related to DLC coatings increase significantly with the coating thickness, while the double-layer capacitance (C_dl) and the capacitance (C_co) of DLC coatings decrease dramatically. All these phenomena can be interpreted in terms of the evolution of the subsurface diamond-like phase (sp³-bond) and the reduction of micro-defects in the DLC coatings with the growing film. As a result, an increase in the corrosion potential (E_c) with the DLC coating thickness was also detected using the Tafel technique. In consequence, the DLC coatings can improve significantly the anti-corrosion properties of AlTiC substrates when the coating thickness is more than a few tens of nanometres.     

Nano-scratch and fretting wear study of DLC coatings for biomedical application

The generation of wear particles is now considered one of the most important failures in total arthroplasty. It is especially needed to study damage process of the particles at slight movement and lower load for long-term service of implanted materials. The wear and abrasion behavior of particles on Ti–6Al–4V coated with diamond-like carbon (DLC) were appropriately simulated in the present paper by fretting wear and nano-scratch test. The coatings with a thickness of 2.5 μm were deposited with an r.f.-plasma enhanced chemical vapor deposition method. The analytic techniques employed to assess DLC coatings characterization include SEM, AFM, Raman and IR spectroscopy. Assessment of hardness, elastic modulus, abrasion and adhesion of the coatings were performed using a Nano Indenter XP system with attachments of continuous stiffness measurements (CSM) and lateral force measurements (LFM). Tribological properties of the coatings were evaluated by a fretting wear test. It was concluded that the DLC coatings had a smooth surface morphology with a rms of 6.8 nm and possessed good adhesion to the substrate, they recovered fully elastic at lower load (60 mN) and were ploughed and delaminated only partially at higher load (400 mN). Nevertheless, there was wear debris concurrently generated during the nano-scratch and fretting test, which was more evident at high loads for a definite coatings, indicating an essential necessity of the work to improve the wear resistant of the coatings to avoid the generation of wear debris. The friction coefficient of DLC coatings against corundum obtained by fretting test decreased with the increase of relative humidity, it was below 0.1 in an aqueous condition, this may be beneficial to their biomedical applications in body fluids.     

Effects of thermal annealing and Si incorporation on bonding structure and fracture properties of diamond-like carbon films

The effects of thermal annealing and Si incorporation on the structure and properties of diamond-like carbon (DLC) films were investigated. As-deposited DLC film (DLC) and Si incorporated DLC film (Si-DLC), both with and without thermal annealing, were analyzed for bonding structure, residual stress, film thickness, elastic modulus and fracture properties using Raman spectroscopy, wafer curvature, nanoindentation, four-point bend fracture testing, and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy clearly showed that thermal annealing of DLC films promotes more sp² bonding character, whereas Si incorporation into the films promotes more sp³ bonding character. Interfacial fracture energies, film hardness and elastic modulus, and residual film stress were all found to vary strongly with the degree of sp³ bonding in the DLC film. These changes in mechanical properties are rationalized in terms of the degree of three dimensional inter-links within the atomic bond network.     

Nanotribological study of PECVD DLC and reactively sputtered Ti containing carbon films

Amorphous carbon film, also known as DLC film, is a promising material for tribological application. It is noted that properties relevant to tribological application change significantly depending on the method of preparation of these films. These properties are also altered by the compositions of these films. DLC films are well known for their self-lubricating properties, as well. In view of this, the objective of the present work is to compare the tribological properties of diamond like carbon (DLC) film obtained by plasma enhanced chemical vapour deposition (PECVD) with the Ti containing nanocrystalline carbon (Ti/a-C:H) film obtained by unbalanced magnetron sputter deposition (UMSD) in nN load range. Towards that purpose, DLC and Ti/a-C:H films are deposited on silicon substrate by PECVD and UMSD processes respectively. The microstructural features and the mechanical properties of these films are determined by scanning electron microscope (SEM), transmission electron microscope (TEM) and nano indenter. The surface topographies and the friction force surfaces of these films are evaluated by means of an atomic force microscope (AFM). The results show that although PECVD DLC film has higher elastic modulus and higher hardness than UMSD Ti/a-C:H film, the surface roughness and the friction coefficient of PECVD film is significantly higher than that of UMSD Ti/a-C:H film.     

Influence of plasma nitriding treatment on the adhesion of DLC films deposited on AISI 4140 steel by PVD magnetron sputtering

Duplex surface treatments composed of diamond like carbon (DLC) coating followed by plasma nitriding have drawn attention for a while. In this study, AISI 4140 steel substrates were plasma nitrided at different treatment temperatures and times. Then, DLC films were deposited on both untreated and plasma nitrided samples using PVD magnetron sputtering. The effect of different plasma nitriding temperatures and times on the structural, mechanical and adhesion properties of DLC coatings was investigated by XRD, SEM, microhardness tester and scratch tester, respectively. It was found that surface hardness, intrinsic stresses, layer thickness values and phase distribution in modified layers and DLC coating were the main factors on adhesion properties of duplex coating system. The surface hardness and residual stress values of AISI 4140 steel substrates significantly increased with both DLC coating and duplex surface treatment (plasma nitriding + DLC coating). Increasing plasma nitriding temperature and time also increased the diffusion depth and the thickness of modified layers. Hard surface layers led to a significant improvement on load bearing capacity of the substrate material. However, it was also determined that the process parameters, which provided lower intrinsic stresses, improved the adhesion properties of the duplex coating system.     

Evaluation of the elastic-plastic properties of SiCN coating system by finite element simulations

The elastic properties of SiCN coating on substrates can be evaluated by nano-indentation test, however, it is challenging for experiments to evaluate the plastic performance of SiCN coating. Finite element (FE) is a numerical method for investigating in-depth mechanical behavior of various structures. In this paper, a contact model between Berkovich indenter and SiCN/Si system is established by FE method. The stress-strain behavior of SiCN coating is obtained by comparing the calculated P-h curves with experimental results. The indentation depth dependent elastic modulus and hardness of the SiCN coating are calculated from the P-h curves and are close to the experimental data. When the indentation depth is in excess of 10% of the coating thickness, the mechanical properties of SiCN coating tend to be influenced by the Si substrate, which also consists with experiments. The proposed approach provides an efficient tool to predict the mechanical properties of SiCN coating.     

Preparation and characterization of silver nanocomposite textile

Nanostructured silver films of different thicknesses were deposited on surfaces of polypropylene nonwovens by magnetron sputter coating to obtain antibacterial and electrical conductive properties. The surface morphology of nanostructured silver films was investigated by atomic force microscopy (AFM). The antibacterial properties of the nonwovens coated with relatively thinner films were evaluated using the shake flask test. The conductivity of the nonwovens coated with relatively thicker films was examined using an ohm-meter. The results of the antibacterial test revealed that the antibacterial performance improved gradually as the film thickness increased from 0.5 to 3 nm. It is believed that the total amount of silver ions released from the coating was increased along with the increase in film thickness. As sputtering time prolonged, the grain sizes of the silver particles were increased and the coating became more compact. The results of the electrical conductivity test showed that the increased film thickness led to the improved electrical conductivity when the film was relatively thicker. The AFM images clearly revealed the change in surface morphology formed by sputter coating. The growth and coverage of the coating layer contributed to the improvement in its antibacterial and conductive properties.     

Fabrication of DLC thin films with improved diamond-like carbon character by the application of external magnetic field

Diamond-like carbon (DLC) thin films were grown on Si-(100) substrates by a magnetically-assisted pulsed laser deposition (PLD) technique. The role of magnetic field on the structural, morphological, mechanical properties and deposition rate of DLC thin films has been studied. The obtained films were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM) and nanoindentation techniques. It was found that the diamond-like character, thickness and deposition rate of the DLC films increase in the presence of magnetic field. The films deposited under magnetic field exhibit a denser microstructure and smoother surface with lower surface roughness. Meanwhile, the mechanical properties of the magnetically processed DLC thin films experience an improvement, relative to the conventionally processed ones. It seems that the DLC films deposited under magnetic field can be better candidate for hard and wear resistance coating applications.     

A method of determining the elastic properties of diamond-like carbon films

The elastic properties of diamond-like carbon (DLC) films were measured by a simple method using DLC bridges which are free from the mechanical constraints of the substrate. The DLC films were deposited on a Si wafer by radio frequency (RF) glow discharge at a deposition pressure of 1.33 Pa. Because of the high residual compressive stress of the film, the bridge exhibited a sinusoidal displacement on removing the substrate constraint. By measuring the amplitude with a known bridge length, we could determine the strain of the film which occurred by stress relaxation. Combined with independent stress measurement using the laser reflection method, this method allows the calculation of the biaxial elastic modulus, E/(1−ν), where E is the elastic modulus and ν is Poisson's ratio of the DLC film. The biaxial elastic modulus increased from 10 to 150 GPa with increasing negative bias voltage from 100 to 550 V. By comparing the biaxial elastic modulus with the plane–strain modulus, E/(1−ν²), measured by nano-indentation, we could further determine the elastic modulus and Poisson's ratio, independently. The elastic modulus, E, ranged from 16 to 133 GPa in this range of the negative bias voltage. However, large errors were incorporated in the calculation of Poisson's ratio due to the pile up of errors in the measurements of the elastic properties and the residual compressive stress.     

Effect of nitrogen concentrations on optical,structural and mechanical properties of self organized a-C:N films

Low friction and surface hardness has become an important aspect to study and understand surface engineering of diamond like coating. Investigation of structural and mechanical properties of nitrogenated amorphous Diamond Like Carbon coating has been done. The cross-sectional microstructures, elemental compositions and various phase constituent of the coated layers under different processing conditions have been characterized. Films are deposited in presence of 5%–20% with the increasing rate of 5% and 40% of N₂ partial pressure along with Ar gas. 20% N₂ pressure shows a critical behavior in Raman spectroscopy and XPS. In this condition the film shows more uniform coating with vertical growth structures as well as brittle behavior. The micro-structural changes on the surface due to migration of N₂ and its related surface properties have been examined. AFM studies clearly show that the percentage change in average roughness decreases to 17% as the film thickness increases at 20% N₂ incorporation. The positive changes in its mechanical properties have been observed by Nano-indentation techniques. Significance of DLC coating in this condition is clearly seen with the increasing sp³compositions by XPS analysis. All results have been correlated and hence critical range of nitrogen partial pressure has been observed between 20%-23% to give similar sp³ fraction and hence properties that of pure DLC films.     

A facile one‐step synthesis of flame‐retardant coatings on cotton fabric via ultrasound irradiation

This article reports a facile one‐step methodology to increase fire resistance properties of cotton fabric. The flame‐retardant coating for cotton fabric was synthesized with methyltriethoxysilane and organophosphates (M102B) through an ultrasound irradiation process. The coating structure and surface morphology of uncoated and coated fabrics were investigated by Fourier transform infrared spectroscopy and scanning electron microscope, respectively. The flame‐retardant properties, bending modulus, air permeability and thermal stability were studied by vertical burning test, cantilever method, air permeability test and thermogravimetric analysis (TGA). As a result, the cotton fabric coated with 29.2% (mass increased) of flame‐retardant coating was able to balance the flame retardant property and wearing comfort of the fabrics. The TGA results showed that the residue char of cotton was greatly enhanced after treatment with the coating, which has a high char forming effect on cellulose during testing. Furthermore, flame‐retardant property of coated fabrics did not change significantly after 10 washing cycles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45114.     

Low-temperature stiffening of air plasma-sprayed 7 wt% Y2O3-stabilized ZrO2

Evolution in bending modulus and accompanying microstructure of free-standing air plasma-sprayed Y₂O₃-stabilized ZrO₂ subjected to thermal exposure, from 800°C to 1300°C, has been studied. The bending modulus was measured using custom-made miniaturized cantilevers, which was loaded using a nanoindenter. Variation in the bending modulus was compared with the density change. The coating shows two domains of behavior of modulus variation with density: the low temperature/time domain wherein the bending modulus doubles without measurable change in the density and the high-temperature domain where modulus increases monotonically with density. Finite element (FE) analysis was carried out using cross-sectional micrographs of coatings to measure the elastic modulus of the actual coating and compared with experimentally observed values. The modulus values predicted by FE analysis are 70%-80% higher than the experimentally observed values. An analytical model has been proposed to corelate the microcracks density and elastic modulus, which is in reasonable agreement with the experimentally measured values.     

Improved Sensitivity in the Thermal Investigation of Polymeric Nanophases by Measuring the Resonance Frequency Shift using an Atomic Force Microscope

A novel technique has been developed to measure thermal transitions of polymers with the atomic force microscope (AFM) in the non‐contact mode. The resonance frequency of the AFM cantilever is measured as a function of the temperature, and thermal transitions of a polymer are clearly visible as changes in the resonance frequency/temperature response curve. Using the AFM in this mode allows the determination of the thermal properties of a material at a specific spot on the sample, on a macromolecular scale. This adds a new dimension to the standard thermal analysis techniques, rendering it possible to resolve the individual thermal transitions of different polymer phases, for example in structured multiphase polymers.