Adhesion and Scratch Resistance of Polycarbonate Films on Ferroplate Substrates: Effect of γ-APS Primers

The influence of γ-aminopropyltriethoxysilane (γ-APS) primers on the adhesion and scratch resistance of polycarbonate (PC) films on ferroplate substrates was determined from the critical normal loads at which debonding of the films from the substrates occurred during scratch testing. The critical load was a strong function of the concentration of the aqueous solutions from which the γ-APS primers were adsorbed and of the thickness of the primer films. Thus, the critical normal load increased from 0.09 ± 0.02 N to 0.31 ± 0.07 N as the concentration of the γ-APS solutions increased from 0.05% to 0.2%, respectively. However, the critical load increased only slightly as the solution concentration increased beyond 0.2%. The increase in critical load as concentration of γ-APS solutions increased was related to the formation of an interphase involving chemical reaction and physical entanglement of PC and γ-APS molecules. The critical load for debonding of PC films from the substrates also depended strongly on the temperature at which the γ-APS films were dried before application of the PC films. Thus, the critical normal loads for debonding were 0.31 ± 0.07, 0.20 ± 0.02, and 0.05 ± 0.01 N for γ-APS films that were dried for 15 min at room temperature, 60°C, or 110°C, respectively. The decrease in critical load with increasing drying temperature was attributed to the greater cross-link density in γ-APS films that were dried at elevated temperatures, which limited interdiffusion and physical entanglement of PC and γ-APS molecules. High reaction temperature of γ-APS and PC induced a fragmentation of amine. However, it also increased the probability of amines to react with carbonate because of increasing mobility of PC chains. Optimization of these two factors was required to obtain the greatest adhesion and scratch resistance. Chemical reactions occurring between PC films and γ-APS primers were investigated by reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS) using diphenyl carbonate (DPC) as a model compound. The carbonyl absorption band of neat DPC was observed at 1780 cm^?1. However, two carbonyl bands were observed at 1738 and 1652 cm^?1 in RAIR spectra of γ-APS films that were reacted with DPC and were assigned to urethane and urea groups, respectively. XPS results revealed that urethane was the main reaction product between DPC and γ-APS. It was concluded that urethane groups formed by the reaction of PC with γ-APS were responsible for adhesion and scratch resistance of PC to ferroplate substrates that were primed with γ-APS.     

Adhesion of Injection Molded PVC to Steel Substrates

Interactions occurring at the interface between injection-molded poly (vinyl chloride) (PVC) and steel substrates that were coated with thin films of aminosilanes were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The silane films were formed by adsorption of γ-aminopropyltriethoxysilane (γ-APS) or N-(2-aminoethyl-3-aminopropyl)trimethoxysilane (γ-AEAPS) from 2% aqueous solutions onto polished steel substrates. PVC was injection molded onto the silane-primed steel substrates and annealed at temperatures up to 170°C for times as long as 30 min. PVC was peeled off of the primed steel substrates using a 90° peel test and the substrate failure surfaces were thoroughly rinsed with tetrahydrofuran (THF) and distilled water to remove PVC and other compounds that were not strongly bonded to the substrates. The PVC failure surfaces were characterized by attenuated total reflection infrared spectroscopy (ATR) and PVC rinsed off of the substrate failure surfaces was characterized by transmission infrared spectroscopy. The resulting transmission and ATR spectra showed an absorption band near 1650 cm^-1 that was attributed to unsaturation in PVC. The substrate failure surfaces were characterized by XPS; curve-fitting of N(1s) and Cl(2p) high-resolution spectra showed the formation of amine hydrochloride complexes by protonation of amino groups of the silanes with HCl that was liberated from PVC during the onset of thermal dehydrochlorination. Furthermore, quaternization or nucleophilic substitution of labile pendent allylic chloride groups by amino groups on the silanes took place, thus grafting PVC onto the aminosilanes. It was determined that PVC that had β-chloroallyl groupings along its chains showed better adhesion with steel primed with aminosilanes and that generation of allylic chloride groups in PVC chains was the rate-limiting step in the reaction between PVC and aminosilane. Moreover, the effect of crosslinking of silane films on adhesion between PVC and aminosilane primed steel was investigated and it was concluded that interdiffusion of the polymer phase and the silane phase was also critical in obtaining good adhesion.     

Effect of Adhesion, Film Thickness, and Substrate Hardness on the Scratch Behavior of Poly(carbonate) Films

The effect of adhesion, film thickness, and substrate hardness on the scratch behavior of poly(carbonate) (PC) films was investigated. Films of various thickness were prepared by spin-coating solutions of PC in chloroform onto glass, ferroplate, Al 1100, Al 6022, and Al 6111 substrates. Adhesion between the films and the substrates was controlled by pretreatment of the substrates and the thickness of the films was controlled by the concentration of the PC solutions. Adhesion of the films to the glass substrates was measured by a blister test. Scratch tests were performed using a custom-built, progressive-load scratch tester with interchangeable diamond indenters; the resulting scratches were observed by optical microscopy, atomic force microscopy (AFM), and environmental scanning electron microscopy (ESEM). The critical normal load (i.e., the smallest applied normal load for which delamination of the film from the substrate was observed) was used as a criterion to determine the scratch resistance of the films. It was found that better film/substrate adhesion resulted in a higher critical load for delamination. As film thickness increased, the critical load and, thus, scratch resistance also increased. Substrate hardness had a strong influence on the scratch behavior of the PC films. For a low-hardness substrate (i.e., Al 1100), the work from scratching was mainly consumed by deforming the substrate. In the case of substrates with intermediate hardness (i.e., Al 6022, Al 6111, and ferroplate), the substrates were more resistant to the stresses that were generated in the films; hence, the deformation of the substrates was less severe. A high-hardness substrate (i.e., glass) resisted the applied load and resulted in higher stress concentrations in the films and at the interface. Consequently, a rougher surface inside the scratch track was observed.     

Effect of Adhesion,Film Thickness,and Substrate Hardness on the Scratch Behavior of Poly(carbonate) Films

The effect of adhesion, film thickness, and substrate hardness on the scratch behavior of poly(carbonate) (PC) films was investigated. Films of various thickness were prepared by spin-coating solutions of PC in chloroform onto glass, ferroplate, Al 1100, Al 6022, and Al 6111 substrates. Adhesion between the films and the substrates was controlled by pretreatment of the substrates and the thickness of the films was controlled by the concentration of the PC solutions. Adhesion of the films to the glass substrates was measured by a blister test. Scratch tests were performed using a custom-built, progressive-load scratch tester with interchangeable diamond indenters; the resulting scratches were observed by optical microscopy, atomic force microscopy (AFM), and environmental scanning electron microscopy (ESEM). The critical normal load (i.e., the smallest applied normal load for which delamination of the film from the substrate was observed) was used as a criterion to determine the scratch resistance of the films. It was found that better film/substrate adhesion resulted in a higher critical load for delamination. As film thickness increased, the critical load and, thus, scratch resistance also increased. Substrate hardness had a strong influence on the scratch behavior of the PC films. For a low-hardness substrate (i.e., Al 1100), the work from scratching was mainly consumed by deforming the substrate. In the case of substrates with intermediate hardness (i.e., Al 6022, Al 6111, and ferroplate), the substrates were more resistant to the stresses that were generated in the films; hence, the deformation of the substrates was less severe. A high-hardness substrate (i.e., glass) resisted the applied load and resulted in higher stress concentrations in the films and at the interface. Consequently, a rougher surface inside the scratch track was observed.     

Understanding Hydrolysis and Condensation Kinetics of γ-Glycidoxypropyltrimethoxysilane

Monitoring the kinetics of hydrolysis and condensation of γ-glycidoxypropyltrimethoxy-silane (γ-GPS) was carried out by NMR spectroscopy (²⁹Si-, ¹³C-, and ¹H-). The course of these reactions was followed in 2 wt% aqueous dilution conditions (26% D₂O/74% H₂O), pH 5.4, and temperatures of 26, 50, and 70°C. At ambient temperature, hydrolysis and condensation proceed at very different time scales: a few hours for the hydrolysis versus several weeks for the condensation. Distortionless Enhancement by Polarization Transfer (DEPT) sequences by ²⁹Si- and ¹³C-NMR spectroscopy were optimized for determining the complete spectral assignment for each hydrolysis step, i.e., RSi(OMe)_3-n(OH)_n (with R = (CH₂OCH)CH₂OCH₂CH₂CH₂-;andn = 1, 2, 3). A pseudo-first order rate constant for the first hydrolysis step, T0^(OMe)3 + H₂O → T0^(OMe)2OH + MeOH, was calculated to be 0.026 min^-1. Simultaneously to the condensation reactions, we have observed epoxy ring opening of the glycidyl- group. All three processes (hydrolysis, condensation, and epoxy ring opening) are dramatically accelerated with temperature increases from 26 to 70°C. The activation energy of the epoxy ring opening leading to the formation of a diol structure at the extremity of the glycidoxypropyl- chain was estimated to be 68.4 kJ/mol.     

Ordering and quality factor in 0.95BaZn1/3Ta2/3O3–0.05SrGa1/2Ta1/2O3 production resonators

Ordering of the B-site cations in UMTS (universal mobile telecommunications systems) standard resonator pucks composed of perovskite structured, 0.95BaZn_1/3Ta_2/3O₃–0.05SrGa_1/2Ta_1/2O₃ (BZT–SGT) has been investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD) and powder neutron diffraction (PND). XRD patterns from samples sintered at 1550 °C/2 h but annealed and quenched at 50 °C intervals between 1400 and 1600 °C revealed that the order–disorder phase transition was at 1500 °C. In addition, a peak at 29.5° 2θ attributed to a Ba₈ZnTa₆O₂₄ phase was present due to ZnO loss. Electron diffraction patterns revealed that samples heat treated 1500 °C (including as sintered samples, 1525 °C/2h,) exhibited short-range 1:2 ordering along all <111> directions giving rise to an average short-range face centred cubic structure. Samples annealed and quenched from below 1500 °C showed 1:2 order. To avoid excessive ZnO loss, an annealing temperature was chosen at 1275 °C (for 24 and 168 h). Neutron diffraction data were best refined using two ordered BZT phases with slightly different lattice parameters. TEM revealed a microstructure in each case consisting of 1:2 small ordered domains in the centre of all grains but with every second grain exhibiting a concentric shell composed of an ordered single domain, containing elongated translational (APBs) but not orientational domains. The formation of the concentric ordered shell was attributed to grain boundary migration during grain growth. As-sintered samples gave unloaded quality factors (Q)=54,000 at 2 GHz which rose to 78,000 at 2 GHz after annealing for 24 h. No further improvement in Q was observed for longer annealing times.     

A New Approach to the Copper/Epoxy Joint Using Atmospheric Pressure Glow Discharge

A new approach for adhering copper to an epoxy resin was studied. In this new approach, the copper surface was first treated with hydrogen plasma generated by the atmospheric pressure glow (APG) discharge. Then a thin film of γ-aminopropyltriethoxysilane (γ-APS) was formed on the treated copper surface. The copper oxide formed by air on the copper surface deteriorated the adhesion by forming a weak boundary layer, part of which could separate from the surface. This oxide layer was reduced when an APG hydrogen plasma was applied for a couple of minutes at a frequency of 13.56 MHz and a power input of 200 W. The resulting peel strength at the copper/epoxy interface increased up to ca. 0.9 Kg/cm. Curing temperature of γ-APS was also an important factor in obtaining good adhesion at the copper/epoxy interface, with the highest value of peel strength occurring at a curing temperature of 120°C.     

Hydrothermal Stability of Aluminum/Epoxy Adhesive Bonds

The effect of silane primers on the failure properties of aluminum/epoxy tapered double cantilever beam (TDCB) specimens was determined. TDCB specimens that were tested in air using increasing loads always failed by propagation of cracks along the center of the bondline at G_lc values between 1.58 and 1.80 × 10⁵ mJ/m² whether primers were used or not. However, γ-aminopropyltriethoxysilane (γ-APS) primers had a significant effect on the time to failure of TDCB specimens subjected to static loads in water at 60°C. The time to failure was always increased when the beams were pretreated with dilute aqueous solutions of γ-APS. The pH at which the primers were applied did not affect the failure charactersitics of the beams but heat treating the primer films before bonding did. The longest times to failure were always obtained when the primer films were dried in air at 100°C for about ten minutes. Shorter or longer drying times always resulted in lower times to failure. Increases in time to failure obtained using primed adherends were related to the ability of the primer films to inhibit hydration of the oxide.     

PRODUCT INHIBITION OF WHEY LACTOSE HYDROLYSIS

In the present study, glucose and galactose inhibition effects for β-galactosidase hydrolyzing lactose recovered from whey were investigated. The experiments were carried out in 250 mL of 25 mM phosphate buffer solution containing 1, 1.5, 2, 4, and 6% (w/v) lactose recovered from whey by using a commercial β-galactosidase produced from Kluyveromyces marxianus lactis at a constant temperature of 37°C, pH 6.5, and enzyme concentration of 1 mL/L, in a batch reactor system. The amounts of glucose and galactose added to the reaction solution were 6.25, 12.5, and 25 g/L. A second-order kinetic expression effectively simulated the data of residual lactose concentration with respect to processing time for each experimental condition examined. The Lineweaver-Burk plots showed that the inhibition effects of glucose and galactose were uncompetitive. The inhibition constants (K_i) obtained for glucose and galactose (10.32 g/L and 13.03 g/L, respectively) showed that the glucose was the most effective inhibitor for β-galactosidase.     

State of C-atoms on the modified nanodiamond surface

XPS, EEL, Auger and FTIR spectroscopies were used to testify the influence of chemical treatment upon the state of C-atoms in the core and on the surface of nanodiamond particles. The study was carried out with ND (JSC “Diamond Centre”). The different kinds of treatments were done ex-situ: with air (5 h) at 200 and 400 °C; with hydrogen (5 h) at 800, 850 and 900 °C; with fluorine (48 h) at 20 °C and 0.5 atm. Noticeable change was not found in the state of C-atoms both on the surface and up to 10 monolayers after these treatments. The concentration of F in the sample is equal to  9 at.%. The binding energy of the F 1s differs from the one in functional groups— –CF₂, –CF. Nevertheless FTIR spectra show bands that can be related to С–О, С–F bonds.     

Molecular Structure of the Interphase Formed by Plasma-Polymerized Acetylene Films and Steel Substrates

The molecular structure of the interphase between plasma-polymerized acetylene films and steel substrates was determined using in situ reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). Plasma-polymerized acetylene films were deposited onto polished steel substrates using argon as a carrier gas and inductively coupled, radio frequency (RF)-powered plasma reactors that were interfaced directly to the XPS and Fourier transform infrared (FTIR) spectrometers. RAIR showed that the plasma polymerized films contained large numbers of methyl and methylene groups but only a small number of mono substituted acetylene groups, indicating that there was substantial rearrangement of the monomer molecules during plasma polymerization. Bands were observed near 1020 and 855 cm^-1 in the RAIR spectra that were attributed to skeletal stretching vibrations in C-C-O-Fe groups, indicating that the plasma-polymerized films interacted with the substrate through formation of alkoxide bonds. Another band was observed near 1565 cm^-1 and attributed to carboxylate groups in the interphase between the films and the oxidized surface of the substrate. Results obtained from XPS showed that the surface of the iron substrate consisted mostly of a mixture of Fe₂O₃ and FeOOH and that iron was mostly present in the Fe(III) oxidation state. However, during plasma polymerization of acetylene, there was a tendency for the concentration of FeOOH groups to decrease and for the concentration of Fe(II) to increase, due to the reducing nature of argon/acetylene plasmas. Results from XPS also confirmed the formation of alkoxide and carboxylate groups in the interphase during plasma polymerization of acetylene.     

Evaluation of Mass Transfer Resistances from Drying Experiments

A new approach to experimental evaluation of mass transfer resistances from drying experiments is proposed. A composite model of ginseng root mass transfer, based on one-dimensional treatment of diffusive and convective resistances as additive components of radial mass transfer, was developed. Mass transfer resistance was evaluated from a linear relationship between measured flux and thermodynamic driving force. Partitioning of mass transfer resistance into diffusive (core and skin) and convective (air boundary layer) resistances was done by modification of boundary conditions: (a) high (3 m/s) and low (1 m/s) air velocity; (b) skin removal. Total radial mass transfer resistance was evaluated as (146 ± 6) ∗ 10⁶ s/m at 38°C, significantly decreasing to (48 ± 1.5) ∗ 10⁶ s/m at 50°C. Boundary resistance was evaluated as (54 ± 5) ∗ 10⁶ s/m at 38°C and (26 ± 3) ∗ 10⁶ s/m at 50°C in the entire range of moisture contents. Core and skin resistances were both moisture dependent: core resistance increased from initial value of (6 ± 1) ∗ 10⁶ s/m to (61 ± 6) ∗ 10⁶ s/m toward the end of drying, whereas skin resistance decreased from initial value of (92 ± 5) ∗ 10⁶ s/m to (25 ± 5) ∗ 10⁶ s/m at the endpoint of drying. However, the sum of core and skin resistances, which represents composite diffusive resistance of intact ginseng root, was constant and independent of moisture content: (91 ± 4.6) ∗ 10⁶ s/m at 38°C and (22 ± 1.6) ∗ 10⁶ s/m at 50°C. The relationship between mass transfer resistance R and drying rate factor k = 1/RC was used for verification of the composite model.     

EFFECT OF IMPELLER SPEED AND VISCOSITY ON WHEY LACTOSE HYDROLYSIS AND β-GALACTOSIDASE STABILITY

In the present work, the effects of impeller speed and viscosity on the enzymatic hydrolysis of whey lactose and enzyme inactivation were studied. The experiments were carried out in 250 mL of 25 mM phosphate buffer solution containing 50 g/L whey lactose by using a commercial β-galactosidase produced from Kluyveromyces marxianus in a batch reactor system. The degree of lactose hydrolysis (%) and residual enzyme activity (%) was investigated versus impeller speeds from 100 to 600 rpm and viscosities from 1.005 to 13.43 cp for 30 minutes of processing time. The mathematical models depending on these process parameters were derived using the experimental data of residual lactose concentration and residual β-galactosidase activity. The predicted models have been confirmed with the experimental results.     

Wettability of nanocrystalline diamond films

The wettability of nanocrystalline CVD diamond films grown in a microwave plasma using Ar/CH₄/H₂ mixtures with tin melt (250–850 °C) and water was studied by the sessile-drop method. The films showed the highest contact angles θ of 168 ± 3° for tin among all carbon materials. The surface hydrogenation and oxidation allow tailoring of the θ value for water from 106 ± 3° (comparable to polymers) to 5° in a much wider range compared to microcrystalline diamond films. Doping with nitrogen by adding N₂ in plasma strongly affects the wetting presumably due to an increase of sp²-carbon fraction in the films and formation of C–N radicals.     

Cohesive Zone Models of Polyimide/Aluminum Interphases

The fracture energy required to delaminate PMDA/ODA polyimide films from aluminum substrates was determined using the circular blister test. Films were prepared by spin coating the polyamic acid of PMDA and ODA onto polished aluminum substrates, by vapor co-deposition of PMDA and ODA monomers onto polished aluminum substrates, or by spin-coating the polyamic acid onto polished aluminum substrates that were first coated with thin layers of γ-aminopropyltriethoxysilane (γ-APS). Elastic and elastoplastic analyses were used to extract the fracture energies from the blister test results. Elastoplastic analysis provided fracture energies that ranged from 579 J/m² for spin-coated films on polished substrates to 705 J/m² for vapor-deposited films on polished substrates and to 750 J/m² for spin-coated films on silanated substrates. These values were intermediate between those provided by the two different elastic analyses. Differences in fracture energy determined by the three different analysis methods were related to plastic deformation in the films and, in the case of the two elastic analyses, to differences in the approach used to extract the fracture energy from experimental results. Failure of specimens prepared by spin-coating PMDA/ODA films onto aluminum substrates occurred cohesively within the polymer, near the interface between well imidized polymer in the bulk of the films and poorly imidized polymer in a layer near the aluminum surface. For the case of specimens prepared by vapor codeposition of PMDA and ODA monomers, failure occurred within the vapor deposited films, close to the aluminum/film interface. Failure of spin-coated films on silanated substrates occurred mostly within the γ-APS but leaving 'islands' of polyimide and silane on the aluminum.     

The Mechanism for 3-Aminopropyltriethoxysilane to Strengthen the Interface of Polycarbonate Substrates with Hybrid Organic–Inorganic Sol-Gel Coatings

An aminolysis mechanism is proposed to explain the enhanced adhesion between the interface of a bisphenol-A polycarbonate substrate with an alkoxysilane containing sol-gel coating when 3-aminopropyltriethoxysilane (3-APS) is used as a primer. Both a model solution study and surface analyses of polycarbonate substrates exposed to 3-APS indicate that the latter reacts with the carbonate groups in the polycarbonate chain by forming urethane linkages. With 3-APS bonded to the substrate, a sol-gel coating can be chemically bonded to the substrate through hydrolysis of alkoxysilane groups and subsequent silanol condensation. Consequently, enhanced adhesion between the sol-gel coating and the substrate is achieved.     

Analysis of Thin Films on Metal Surfaces

External reflection infrared spectroscopy was used in combination with other surface analysis techniques such as ellipsometry, Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS) to determine the structure of organofunctional silanes adsorbed onto 2024 aluminum and titanium-6 Al, 4V mirrors. The results obtained indicated that the adsorption of γ-aminopropyltriethoxysilane (γ-APS) onto aluminum was a strong function of pH and adsorption time. Films formed by adsorption of γ-APS at pH = 8.5 were composed of polysiloxanes containing amine hydrochlorides. The structure of films formed by adsorption of γ-APS at pH-10.4 depended on time. Films obtained after one minute were composed of polysiloxanes that did not interact strongly with the oxide but during 15 minutes adsorption the air-formed oxide was dissolved and copper accumulated near the surface of the mirrors. Films formed by the adsorption of γ-glycidoxypropyltrimethoxysilane (γ-GPS) onto aluminum were composed of polysiloxanes that did not interact strongly with the oxide. The structure of films formed by adsorption of γ-APS onto titanium did not depend on adsorption time. Films formed at pH = 10.4 were composed of low molecular weight oligomers that gradually polymerized to polysiloxanes during atmospheric exposure.     

Ambient contamination of poly-crystalline diamond surfaces studied by high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy

In this work we provide direct evidence of hydrogen, carbon and oxygen contamination of poly-crystalline diamond surfaces from ambient conditions and their thermal stability upon vacuum annealing. Deuterated diamond films were exposed to ambient conditions for ~ 3 months and then studied by high-resolution electron energy loss spectroscopy and X-ray photoelectron spectroscopy. Hydrocarbon contaminations posses at least two different binding states which desorb upon annealing to ~ 300 °C and ~ 600 °C. Oxygen contaminations gradually desorb upon annealing to 700–800 °C. It is shown that thermal desorption of contaminations creates sp² carbon atoms on the diamond film surface.     

Microwave dielectric ceramics in the system BaO–Li2O–Nd2O3–TiO2

Ceramics in the system BaO-Li₂O–Nd₂O₃–TiO₂ (BNT–LNT) were prepared by the mixed oxide route. Powders were mixed, milled, calcined and sintered at 1475°C for 4 h. Fired densities decreased steadily along the series from BNT to LNT. The microstructures of samples rich in BNT were dominated by small needle-like grains; the LNT samples comprised larger (6 μm) cubic grains. X-ray diffraction showed that there was a transition from orthorhombic BNT to cubic LNT; small amounts of LNT could be accommodated in BNT, but between 10–20% LNT there was the development of the second phase. Small additions of LNT led to a small increase in relative permittivity, but decreased the dielectric Q-value (from the maximum of 1819 at 4 GHz). As BNT and LNT exhibit negative and positive temperature dependencies of permittivity respectively, the addition of 10–20% LNT to BNT should yield samples with zero temperature dependence of _r Impedance spectroscopy showed that data could only be acquired at elevated temperatures for BNT rich samples (above 500°C), but at modest temperatures (less than 100°C) for the more conductive LNT.     

Electrical ageing of carbon nanotube composite cathode layers

Effect of electrical ageing (EA) on the field emission parameters of thin multiwall carbon nanotube composite (t-MWCNTs-composite) was studied. Initially, t-MWCNTs were mixed with -terpineol and ethyl cellulose and subjected to three roll milling process to obtain t-MWCNTs-composite. Following this, the composite was screen printed on a conducting substrate, annealed for 10 min and employed to the electrical ageing process for a period of 6 h. The ageing, on each cathode layer, was repeated for five times and J–E characteristics have been collected before and after each ageing attempt. The analysis revealed that, the magnitude of threshold turn-on-field gradually increased from its virgin value of 1.223 to 1.968 V µm^− 1 and corresponding mean field enhancement factor, γ_m, gradually decreased from 2700 ± 210 to 1940 ± 30 with a sequential increase in the ageing attempts. The degradation rate, δJ/δt, estimated for untreated and EA samples, indicated that the magnitude of δJ/δt reached to an equilibrium value of ~ 0.785 μA cm^− 2 min^− 1, which shows a stable emission state of the emitters. To investigate the effect of EA on the physical state of the emitters, a few virgin and all EA samples were subjected to scanning electron microscopy, micro Raman spectroscopy and X-ray photoelectron spectroscopy. The details of the analysis are presented.