Thermal effects in poly(hexamethylene adipamide) and polyoxymethylene at high hydrostatic pressures

The dynamic mechanical properties, transition behavior, and morphology of polycarbonate (PC)-polyurethane (PU) semi-interpenetrating polymer networks (semi-IPNs) and linear blends were studied by means of Rheovibron, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Two glass transition temperatures corresponding to polycarbonate and polyurethane were observed and microphase separation was further evident with TEM. In PC/PU semi-IPNs, two glass transition temperatures were shifted inwardly indicating that the interpenetrating network of polyurethane increases the mutual miscibility of PC and PU. The average phase domain was 500Å in semi-IPNs and the phase domains were in the range 1000–6000 Å in linear blends of the corresponding polymers. The compatibilities of PC and PU were greatly influenced by the molecular weight of polyols in PU prepolymer and the ratio of NCO/OH; lower molecular weight polyols and higher NCO/OH ratio resulted in better compatibility, and finer phase domains in PC and PU linear blends and semi-IPNs.     

Soybean Oil-Based Polyurethane Networks: Shape-Memory Effects and Surface Morphologies

Vegetable oil‐based shape‐memory polyurethane networks are an emerging class of bio‐based functional materials with great potential applications. In this study, a series of different structural soybean oil polyols were synthesized, and utilized to fabricate polyurethane networks by reacting with 1,6‐diisocyanatohexane. The soybean oil‐based polyurethanes (SOPUs) were characterized with differential scanning calorimetry (DSC), dynamic mechanical tests (DMA), tensile testing, shape‐memory testing, and atomic force microscopy (AFM). It was found that SOPUs with a preserved triglyceride structure were fixed in a temporary shape at ?20 °C, while others were fixed in temporary shapes at 4 °C. Although the recovery speeds were different, all the samples could completely regain their permanent shapes at 37 °C (human body temperature). Furthermore, different SOPUs exhibited different surface structures, which might provide the materials with additional values.     

不同多元醇聚氨酯弹性体宏观性能的研究

以聚四氢呋喃多元醇（PTMG）、聚己内酯多元醇（PCL）、4,4′-二苯基甲烷二异氰酸酯、1,4-丁二醇和三羟基聚醚多元醇等为主要原料制备了4种聚氨酯（PU）弹性体。采用电子万能试验机、动态力学热分析仪、差示扫描量热仪以及扩展流变仪等设备分析了不同相对分子质量的PTMG和PCL对PU弹性体的力学性能、热性能以及流变性能的影响。结果表明,PCL类PU弹性体的拉伸强度、硬度、平台区弹性模量、软段玻璃化转变温度以及反应体系的表观黏度都偏高,而PTMG类PU弹性体的滞后损失偏高;同一种类多元醇的PU弹性体的各项性能也因相对分子质量的不同而有差异。     

Degradable polyurethane based on star-shaped polyester polyols (trimethylolpropane and ɛ-caprolactone) for marine antifouling

The star-shaped polyester polyols based on initiators (trimethylolpropane or pentaerythritol) and ɛ-caprolactone were prepared by polycondensation reaction. The degradable polyurethane (PU) films were prepared by mixing star-shaped polyester polyols and crosslinker agent (hexamethylene diisocyanate trimer). The hydrolytic degradation and water absorption experiments demonstrated that the PU films could erode in artificial sea water, which were controlled by varying the ratios of ɛ-caprolactone/trimethylolpropane and the arm number of star-shaped polyester polyols. The mechanical properties of PU films and coatings increased with decreasing the ratios of ɛ-caprolactone/trimethylolpropane and increasing the arm number of star-shaped polyester polyols. The surfaces of PU films and coatings kept eroding, which were revealed by scanning electron microscopy. The copper ion release rates from PU coatings reached steady state at about 31 days. The marine field tests of PU coatings demonstrated that the degradable PU coatings based on star-shaped polyester polyols were effective coatings for marine antifouling.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

Conductive shape-memory polyurethane/multiwall carbon nanotube nanocomposite aerogels

Smart nanocomposite aerogels have promising applications. In this work, different percentages of multiwall carbon nanotube (MWCNT) added into synthesized polyurethane (PU) gel in the molten state, using a two-roll mill. By soaking the PU/MWCNT nanocomposite gel into the water, PU/MWCNT hydrogels containing more than 90 wt % of water were prepared. The obtained hydrogels were freeze-dried to produce aerogel counterparts. The aerogels were fully characterized using mercury porosimetry, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM). The electrical percolation threshold of conductive aerogel system was measured. The shape-memory behavior of PU/MWCNT nanocomposite aerogels was evaluated by dynamic mechanical thermal analysis (DMTA). The results of the DMTA showed that by adding 2.75 wt % of MWCNT, the recovery ratio and storage modulus of the PU/MWCNT nanocomposite aerogel increased 42 and 180%, respectively. The electrical conductivity of the system also increased three orders of magnitude at the percolation threshold. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48602.     

Effect of nano ZnO on the phase mixing of polyurethane hybrid dispersions

In the present study series of aqueous polyurethane (PU)/ZnO hybrid dispersions were prepared using dimethylolpropionic acid (bis-MPA) as an ionic center. For this, NCO terminated PU prepolymers with pendent acid groups were prepared first, then different concentrations of nano ZnO powder was incorporated into the PU matrix. The hybrid dispersions were prepared by adding required amount of triethylamine (TEA), water and chain extender. The prepared PU/ZnO hybrid dispersions were casted in a Teflon petri dish and the dried films were used for TGA, DMTA, SEM, gel content and contact angle measurements. The phase mixing behavior was studied from FT-IR peak deconvolution technique and DMTA analysis and the result suggests that phase mixing increases with ZnO content. The DMTA data suggest that the phase mixing and soft segment glass transition increases but storage modulus decreases with increasing with ZnO content. The FT-IR deconvolution result supports to the DMTA analysis. The coating properties like adhesive strength, water absorption, contact angle, gel content and corrosion resistance of the hybrid coatings were also evaluated.     

Influence of aqueous dispersions in place of organic solvents during the synthesis of shape memory polyurethanes on their structure and properties

In this work, the effect of synthesizing shape memory polyurethanes in aqueous dispersions instead of in organic solvents on the structure and properties of the obtained polymers was investigated. Shape memory polyurethanes based on polycaprolactone diol and isophorone diisocyanate were synthesized by two routes: (1) aqueous dispersion (PU/SM_WATER) and (2) dissolution in THF (PU/SM_THF). The samples were analyzed by infrared spectroscopy (FTIR), X‐ray diffraction (XRD), static light scattering (SLS), atomic force microscopy (AFM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and mechanical tests. The aqueous dispersion method led to the production of polyurethanes with a higher degree of phase separation and a higher degree of crystallinity. The morphology of the obtained polyurethanes demonstrated that PU/SM_WATER displays a structure with better defined phase separated domains. The polyurethanes exhibited similar average molar masses, soft segment glass transitions (T_gs) and mechanical properties. The lower degrees of phase separation and crystallinity of the PU/SM_THF led to lower values for the shape memory properties (shape recovery ratio (R_r)). The observed changes in the structure of the polyurethanes due to the replacement of organic solvent by an aqueous dispersion during their syntheses confirmed the preparation of shape memory polyurethanes with enhanced shape memory properties. POLYM. ENG. SCI., 57:432–440, 2017. © 2016 Society of Plastics Engineers     

Surfactant-free core–shell hybrid latexes from soybean oil-based waterborne polyurethanes and poly(styrene-butyl acrylate)

Novel surfactant-free core–shell hybrid latexes have been successfully synthesized by seeded emulsion polymerization of 10–60 wt% vinyl monomers (styrene and butyl acrylate) in the presence of a soybean oil-based waterborne polyurethane (PU) dispersion as seed particles. The soybean oil-based waterborne polyurethanes, synthesized by reacting isophorone diisocyanate with methoxylated soybean oil polyols and dimethylol propionic acid, form the latex shell, serve as a polymeric high molecular weight emulsifier, while the vinyl polymers form the core. The structures and thermal and mechanical properties of the PU dispersions and the resulting core–shell latexes have been characterized by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and measurement of the mechanical properties. The core–shell hybrid latex films show a significant increase in thermal stability and mechanical properties when compared with the pure polyurethane films, and exhibit a change in mechanical behavior from elastomeric polymers to tough and hard plastics, due to grafting and crosslinking in the hybrid latexes.     

Shape memory segmented polyurethanes: dependence of behavior on nanocellulose addition and testing conditions

The response of synthesized shape memory segmented polyurethanes (PUs) was affected by the addition of cellulose nanocrystals, as well as by the various conditions selected to carry out thermomechanical cyclic tests. The PUs were synthesized from an α‐hydro‐ω‐hydroxy‐poly(ethylene oxide), tolylene‐2,4‐diisocyanate and 1,4‐butanediol as chain extender. Nanocomposites were prepared by mixing a suspension of cellulose nanocrystals in N,N‐dimethylformamide with the thermoplastic PU dissolved in the same organic solvent. The thermal properties of the neat PU and resulting composites were examined using differential scanning calorimetry. It was found that cellulose addition increases the PU soft segment melting and crystallization temperatures and the degree of crystallinity of this phase. Shape memory behavior was studied using cyclic thermal tensile tests. Both neat PU and composites exhibit shape memory properties, with fixity and recovery values that depend on heating temperature, imposed deformation, deformation rate and nanofiller addition. Copyright © 2011 Society of Chemical Industry     

Improving the mechanical,thermal and electrical properties of polyurethane- graphene oxide nanocomposites synthesized by in-situ polymerization of ester-based polyol with hexamethylene diisocyanate

Many polyols or diols have been used for the synthesis of polyurethanes (PU), however, to the best of our knowledge, PU-graphene oxide (GO) nanocomposites synthesized with ester-based polyols have been rarely studied. In this work ester-based polyol synthesized by the reaction of adipic acid and 1,4 butane diol, was in-situ polymerized with hexamethylene diisocyanate (HDI) and GO to prepare PU-GO nanocomposites. The content of GO was changed from 1 to 2.5 wt% and its effect on the mechanical, thermal and electrical properties of the samples were examined. The presence of GO more than 1.5% in the nanocomposites resulted in brittle samples and reduced the tensile strength, however, the Young’s modulus of the samples containing 1 and 1.5% was increased to 11 and 12.08-fold (275 and 302 MPa) compared to the neat PU (25 MPa), respectively. The shore A hardness of the samples was increased from 86 for PU to 96 for PUGO-1.5. The abrasion resistance of the samples was decreased by increasing the GO content. Results of the thermogravimetric analysis showed that higher amounts of GO increase the thermal stability of the samples. The chemical and physical interactions between the surface of GO nanolayers and the PU chains were confirmed by FTIR spectroscopy. The dynamic mechanical analysis of the samples showed that GO nanolayers decreased the molecular motions of the PU chains in the nanocomposites which were noticed by shifting the glass transition to the higher temperatures.     

Polyurethane/amino‐grafted multiwalled carbon nanotube nanocomposites: Microstructure,thermal, mechanical,and rheological properties

A mixture of two different polyols, (polytetramethylene ether glycol and polydimethylsiloxane), were employed to synthesize a new structure of polyurethane (PU) with methylene diphenyl diisocyanate (MDI) and 1,4‐butanediol as chain extender. PU nanocomposites containing variable amount (0.3, 0.5, 1, and 3 wt %) of amino‐grafted multiwalled carbon nanotubes (NH₂‐MWNT) were prepared via in situ polymerization. The dispersion of NH₂‐MWNT into polymer matrix was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Fourier transform infrared spectroscopy (FT‐IR) confirmed the urethane‐urea chemical bonding between the PU chains and the NH₂‐MWNT. Thermal stabilities of the nanocomposites were examined with thermogravimetric analysis (TGA) and the results indicated a remarkable improvement with increasing NH₂‐MWNT contents. The results of dynamic mechanical thermal analysis (DMTA) including storage modulus (E′) and glass transition temperature (T_g), as well as tensile properties demonstrated that the yield strength, strain‐at‐break, and young modulus were enhanced by increasing NH₂‐MWNT content. Rheological behavior including complex viscosity and storage and loss moduli of the PU nanocomposites improved with increasing NH₂‐MWNT loading, as well. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44411.     

Effect of cardanol diol on the synthesis,characterization, and film properties of aqueous polyurethane dispersions

This article reports on the effect of a diol prepared from a renewable resource, cardanol, on the synthesis, film formation and film properties of aqueous polyurethane dispersions. The PU dispersions were prepared by the acetone process from poly(tetramethylene ether)glycol (PTMEG) and isophorone diisocyanate (IPDI) prepolymer at constant NCO/OH ratio of 1:1.1. Dispersions with two different concentrations of cardanol diol (OH value 140 mg KOH/g) were prepared through chain extension and characterized for solid content, particle size, and particle-size distribution (PSD). Free films were prepared by casting and were studied for their thermal, mechanical, viscoelastic, and hydrophobic properties. Due to the broad PSD, the dispersions containing cardanol diol exhibit better film formation property in comparison to the butane diol chain-extended PU. Soft and flexible films were obtained using cardanol diol as chain extender, whereas brittle film was obtained with butane diol chain extender. Morphological characterization using atomic force microscopy (AFM) and scanning electron microscopy (SEM) suggests a heterogeneous and amorphous nature of the polyurethanes-containing cardanol diol. The thermomechanical and viscoelastic properties show that incorporation of cardanol diol decreases the glass transition temperature and modulus of the films but enhances the properties like thermal stability, hydrophobicity, elongation, etc., of the polyurethane films.     

Thermal,mechanical and biodegradation properties of pure,epoxidized and methoxylated castor oil based polyurethane

A series of biodegradable polyurethane (BIOU) elastomers were obtained by chain extension of polyurethane (PU) prepolymer with the addition of castor oil (CAO), epoxidized CAO (ECAO) or methoxylated CAO (MCAO). The BIOU elastomers obtained were characterised by Fourier transform infrared, scanning electron microscopy, differential scanning calorimetry and tensile tester. The melting peak of BIOU became undetectable with an increase in the content of the chain extender regardless of its type. Some BIOU films, including BIOU-CAO16wt%, BIOU-ECAO16wt% and BIOU-MAO16wt%, showed elastomeric properties with higher tensile strength than pure PU. However the elongation at break and hardness of samples decreased with CAO, ECAO and MCAO content. The biodegradation was also measured by the modified Sturm test method of the BIOU films in a cultured medium with Pseudomonas aeruginosa E7 and Lysobacter soli LW1-1 strains at 37°C. As the increasing three types of chain-extenders the degree and rate of biodegradation of BIOU increased as compared with pure PU. But even then the biodegradability of BIOU by both the strains did not exceed 26% during the modified Sturm test for 31 days.     

Triple‐shape memory properties of polyurethane/polylactide–polytetramethylene ether blends

A facile method to prepare triple‐shape memory polymers was developed by blending polyurethane and polylactide–polytetramethylene with well‐separated glass transition temperatures. The thermal properties of the blends were characterized using modulated differential scanning calorimetry and differential scanning calorimetry. Field emission scanning electron microscopy, Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction were used to characterize the microstructures and crystal structures of the blends. The mechanical properties were also evaluated. The versatile triple‐shape memory effect and quantitative shape memory response were evaluated by consecutive thermal mechanical experiments based on a two‐step programming process and subsequent progressive thermal recovery. The results show that the blends have phase‐separated microstructures resulting in an ability to fix two temporary shapes independently and can recover to their original shapes sequentially. The blends have excellent triple‐shape memory properties and may have some applications in multi‐shape coatings, adhesives, films and temperature sensing or actuating elements. © 2015 Society of Chemical Industry     

A study of the morphology of polyurethane–polystyrene interpenetrating polymer networks by means of small angle X‐ray scattering,modulated‐temperature differential scanning calorimetry,and dynamic mechanical thermal analysis techniques

The morphology of polyurethane–polystyrene (PU‐PS) (60 : 40 by weight) interpenetrating polymer networks (IPNs), in which internetwork grafting via 2‐hydroxyethyl methacrylate resides (HEMA) (1, 2.5, and 10 wt %, respectively) in the polystyrene networks has been studied by means of small angle X‐ray scattering (SAXS), modulated‐temperature scanning calorimetry (M‐TDSC), and dynamical mechanical thermal analysis (DMTA) techniques. With increasing internetwork grafting, the average size of domains became smaller (SAXS data) and the degree of component mixing increased (M‐TDSC and DMTA results). For the PU‐PS (60 : 40 by weight) IPN with 10% HEMA, the DMTA tan δ‐temperature plot showed a single peak. This DMTA result implied that the morphology of this PU‐PS IPN is homogeneous. However, the M‐TDSC data showed that three PU‐PS (60 : 40) IPNs samples (with 1, 2.5, and 10 wt % HEMA, respectively) were phase separated. For the three IPN samples, the correlation length of the segregated phases, obtained from SAXS data based on the Debye–Bueche method, did not show distinct differences. With increasing internetwork grafting, the scattered intensity decreased. This study concluded that for these IPNs, SAXS is sensitive to the size of domains and component mixing, but no quantitative analysis was given for the component mixing. M‐TDSC is suitable to be used to quantify the degree of component mixing or the weight fraction of interphases, and DMTA is sensitive to damping behavior and to phase continuity. However, DMTA cannot provide quantitative information about the degree of component mixing or the weight (or volume) fraction of the interphases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1958–1964, 2001     

Effect of cationic group content on shape memory effect in segmented polyurethane cationomer

To illustrate the importance of cationic groups within hard segments on shape memory effect in segmented polyurethane (PU) cationomers, the shape memory polyurethane (SMPU) cationomers composed of poly(ε‐caprolactone) (PCL), 4,4′‐diphenylmethane diisocyanate (MDI), 1,4‐butanediol (BDO), and N‐methyldiethanolamine (NMDA) or N,N‐bis(2‐hydroxyethyl)isonicotinamide (BIN) were synthesized. The comparison of shape memory effect between NMDA series and BIN series was made. The relations between the structure and shape memory effect of the two series of cationomers with various ionic group contents were investigated. It is observed that the stress at 100% elongation is reduced for these two series of PU cationomers with increasing ionic group content. Especially for NMDA series, the stress reduction is more significant. The fixity ratio and recovery ratio of the NMDA series can be improved simultaneously by the insertion of cationic groups within hard segments, but not for the BIN series. Characterizations with DSC and DMA suggest that the crystallibility of soft segment in SMPU cationomers was enhanced by incorporation of ionic groups into hard segments, leading to a relative high degree of soft segment crystallization; compared with the corresponding nonionomers, incorporation of charged ionic groups within hard segments can enhance the cohesion force among hard segments particularly at high ionic group content. This methodology offers good control of the shape memory characteristic in thin films and is believed to be beneficial to the shape memory textile industries. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 545–556, 2007     

Co-extruded multilayer shape memory materials: Nano-scale phenomena

Shape memory polymers (SMPs), which demonstrate the ability to possess multiple shapes, are traditionally produced from copolymers and recently from blends. These materials often have phase separated morphologies that possess domain sizes on either the nano- or micro-scale. The observed properties, specifically the shape memory behavior, can be significantly altered by a change in the domain size; however, doing this often requires modification to the materials or material production process. Forced assembly multilayer co-extrusion was used to produce shape memory materials with a continuous layered structure that can be easily tailored to cover layer thicknesses ranging from the nano- to the micro-scale. Upon decreasing the layer thickness of polyurethane/polycaprolactone (PU/PCL) layered films, improvement in the shape fixity and recovery ratios tracked with layer thickness. The improvement in properties was attributed to a change in the PCL crystal orientation from randomly oriented in microlayers to in-plane lamella orientation in nanolayers.     

Growth of amorphous,anatase and rutile phase TiO2 thin films on Pt/TiO2/SiO2/Si (SSTOP) substrate for resistive random access memory (ReRAM) device application

Memory structures play a basic role in providing integrated circuits of powerful processing capabilities. Even most powerful processors have nothing to offer without an accompanying memory and importantly, the development of mobile devices is dependent on the continual improvement of memory technology. Herein, we report the synthesis of TiO₂ thin films on SSTOP (Pt/TiO₂/SiO₂/Si) substrate via physical vapour deposition process for the first time. The layers consisted of Si, SiO₂, TiO₂ and Pt, hence the SSTOP shorthand is used throughout the text. Three different phases of TiO₂ thin films were obtained, i.e. amorphous, anatase and rutile phases, by controlling the reaction parameters which were examined by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM) and Raman-scattering spectroscopy in order to understand the crystallographic, morphological, compositional and scattering properties. The detailed studies confirmed the formation of various crystal phases of titania. The grown thin films on SSTOP substrates were further utilized to fabricate resistive random access memory (ReRAM) devices and the initial electrical screening was performed on capacitor-like structures which were prepared using platinum top electrodes (diameter = 250 μm) on a 14 × 14 array metal contact mask. Current-Voltage (I–V) measurements were implemented employing a range of current compliances (IC). The detailed electrical characterizations revealed that the forming field for a switchable unipolar device was found to be greatest on rutile titania and lowest on the amorphous titania phase. Similarity, the resistive contrast was greatest on the rutile titania phase and lowest on the anatase titania phase.