Innovative Green Chemistry Approach to Synthesis of Sn2+-Metal Complex and Design of Polymer Composites with Small Optical Band Gaps

In this work, the green method was used to synthesize Sn²⁺-metal complex by polyphenols (PPHs) of black tea (BT). The formation of Sn²⁺-PPHs metal complex was confirmed through UV-Vis and FTIR methods. The FTIR method shows that BT contains NH and OH functional groups, conjugated double bonds, and PPHs which are important to create the Sn²⁺-metal complexes. The synthesized Sn²⁺-PPHs metal complex was used successfully to decrease the optical energy band gap of PVA polymer. XRD method showed that the amorphous phase increased with increasing the metal complexes. The FTIR and XRD analysis show the complex formation between Sn²⁺-PPHs metal complex and PVA polymer. The enhancement in the optical properties of PVA was evidenced via UV-visible spectroscopy method. When Sn²⁺-PPHs metal complex was loaded to PVA, the refractive index and dielectric constant were improved. In addition, the absorption edge was also decreased to lower photon. The optical energy band gap decreases from 6.4 to 1.8 eV for PVAloaded with 30% (v/v) Sn²⁺-PPHs metal complex. The variations of dielectric constant versus wavelength of photon are examined to measure localized charge density (N/m*) and high frequency dielectric constant. By increasing Sn²⁺-PPHs metal complex, the N/m* are improved from 3.65 × 10⁵⁵ to 13.38 × 10⁵⁵ m⁻³ Kg⁻¹. The oscillator dispersion energy (E_d) and average oscillator energy (E_o) are measured. The electronic transition natures in composite films are determined based on the Tauc’s method, whereas close examinations of the dielectric loss parameter are also held to measure the energy band gap.     

Dielectric properties and surface morphology of swift heavy ion beam irradiated polycarbonate films

Swift heavy ion beam irradiation induces modification in the dielectric properties and surface morphologies of polycarbonate (PC) films. The PC films were irradiated by 55 MeV energy of C⁵⁺ beam at various ions fluences ranging from 1 × 10¹¹ to 1 × 10¹³ ions cm^?2. The dielectric properties (i.e., dielectric constant, dielectric loss, and AC conductivity) and surface morphologies of pristine and SHI beam irradiated PC films were investigated by dielectric measurements, atomic force microscopy (AFM), and optical microscopy. The dielectric measurements show that the dielectric constant, dielectric loss, and AC conductivity increase with ion fluences and temperature, however, the dielectric constant and AC conductivity decrease while dielectric loss increases with frequency. AFM shows the increase in average roughness values with ion fluences. The change of color in PC films has been observed from colorless to yellowish and then dark brown with increases of ion fluence by using optical microscopy.     

Novel conducting poly(3,4-ethylenedioxythiophene) – Graphene nanocomposites with gigantic dielectric properties and narrow optical energy band gap

Novel nanocomposites, consisting of conducting poly(3,4-ethylenedioxythiophene) [PEDOT] and graphene nanoplatelets [GNPs], were successfully synthesized by in-situ chemical-oxidative polymerization of 3,4-ethylenedioxythiophene [EDOT] using ammonium peroxydisulfate as an oxidizing agent. The formation of PEDOT and its incorporation onto the surface of GNPs were confirmed by scanning electron microscopy, Fourier-transform infrared-spectroscopy, and X-ray diffraction. The optical energy band gap, E_g^opt, was determined by UV–Vis spectroscopy. Dielectric constant and loss as well as AC electrical conductivity, σ_AC, were determined in the frequency range from 10 Hz to 8 MHz. The PEDOT-GNP nanocomposites were found to have extremely large dielectric constant, ε′, significantly high σ_AC, and narrow E_g^opt values. In particular, PEDOT-GNP nanocomposite with 10 wt% GNP has a gigantic dielectric constant of the order of 9 × 10⁵ at 1 kHz and a narrow optical energy band gap of 1.26 eV. The ε′ values (10⁸ to 10⁵ in the frequency range from 10 Hz to 5 MHz) of PEDOT-10 wt% GNP are the highest among those reported in the literature for carbon based polymer nanocomposites. The massive quantity of micro-capacitors formed in the nanocomposites, prior to the creation of conductive networks, leads to the gigantic dielectric properties. The ε′ and σ_AC values of PEDOT-10 wt% GNP nanocomposite were about 90 and 400 times larger than those of pure PEDOT. Our method should be particularly promising in the development of new materials for high energy storage applications.     

Electrical and Optical Properties of O6+ Ion Beam–Irradiated Polymers

Variations in dielectric, optical, and structural properties of Lexan and Kapton-H irradiated to 80 MeV O⁶⁺ ion beam were analyzed at different fluences ranging from 10¹¹ to 10¹³ ions/cm² with a scanned beam current of 1 pnA. The structural modifications were characterized with the help of FT-IR and UV-vis spectroscopies. The electrical properties were investigated through capacitance and dielectric loss variations in ion-irradiated and pristine polymers at different frequencies. UV-vis absorption analysis indicates a decrease in the band gap energy in the two polymers. However, the decrease is much more prominent in Lexan (30%) than in Kapton-H (2.5%). The dielectric constant does not show appreciable variations after ion irradiation; however, a small increase has been noticed. An overall increase in the intensities of some typical bonds and stretching was observed in the FT-IR spectra of the pristine and ion-irradiated polymers.     

Ultra-sensitive quantification of lysozyme based on element chelate labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry

In this study, an ultra-sensitive method for the quantification of lysozyme based on the Gd³⁺ diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry (CE–ICP–MS) was described. The Gd³⁺-tagged lysozyme was effectively separated by capillary electrophoresis (CE) and sensitively determined by inductively coupled plasma mass spectrometry (ICP–MS). Based on the gadolinium-tagging and CE–ICP–MS, the lysozyme was determined within 12 min with an extremely low detection limit of 3.89 attomole (3.89 × 10⁻¹¹ mol L⁻¹ for 100 nL of sample injection) and a RSD < 6% (n = 5). The proposed method has been successfully used to detect lysozyme in saliva samples with a recovery of 91–106%, suggesting that our method is sensitive and reliable. The success of the present method provides a new potential for the biological assays and sensitive detection of low-abundant proteins.     

Thermal, mechanical and electrical properties on the styrene-grafted and subsequently sulfonated FEP film induced by electron beam

This paper examined the mechanical and electrical properties of poly(tetrafluoroethylene-co-hexafluoropropylene: FEP) film modified by electron beam (EB). The simultaneous irradiation method with EB was adopted for the grafting of styrene and subsequent sulfonation onto FEP film. The thermal and mechanical characteristics of the irradiated FEP film, and also those of the grafted and sulfonated FEP films, were investigated by TGA, FT-IR spectrometer, and Instron. The simultaneous irradiation with EB facilitated the homogeneous grafting, as well as a high degree of grafting with a maximum value of around 60%, thereby allowing accurate control of the degree of grafting at doses ranging from 10 to 100 kGy.The grafting or sulfonation decreased the thermal stability of FEP, whereas it considerably increased its mechanical properties. The high radiation resistance of virgin FEP up to a dose of 100 kGy enabled the sulfonation of FEP film to considerably reinforce its polymeric structures except of 10 kGy, thereby increasing its tensile strength at 30 kGy by two-fold compared to that of the virgin FEP film. The ion conductivity (IC) and ion-exchange capacity (IEC) values of the FEP membrane (125 μm thick), which were dependant on the degree of grafting, were 0.25 S cm⁻¹ and 2.4 mmol/g, respectively, at 59.2% of the degree of grafting and were superior to those of the commercialized Nafion membrane (IC, 0.12 S cm⁻¹; IEC, 0.9-1.0 mmol/g).     

Optical band gap and conductivity measurements of polypyrrole-chitosan composite thin films

Electrical conductivity and optical properties of polypyrrole-chitosan（PPy-CHI） conducting polymer composites have been investigated to determine the optical transition characteristics and energy band gap of composite films.The two electrode method and I-V characteristic technique were used to measure the conductivity of the PPy-CHI thin films,and the optical band gap was obtained from their ultraviolet absorption edges.Depending upon experimental parameter,the optical band gap（E_g） was found within 1.30-2.32 eV as estimated from optical absorption data.The band gap of the composite films decreased as the CHI content increased.The room temperature electrical conductivity of PPy-CHI thin films was found in the range of 5.84×10^-7-15.25×10^-7 S·cm^-1 depending on the chitosan content.The thermogravimetry analysis（TGA） showed that the CHI can improve the thermal stability of PPy-CHI composite films.     

Achieving fast convergence of ab initio free energy perturbation calculations with the adaptive force-matching method

This paper studies the possibility of improving the convergence of ab initio free energy perturbation (FEP) calculations by developing customized force fields with the adaptive force-matching (AFM) method. The ab initio FEP method relies on a molecular mechanics (MM) potential to sample configuration space. If the Boltzmann weight of the MM sampling is close to that of the ab initio method, the efficiency of ab initio FEP will be optimal. The difference in the Boltzmann weights can be quantified by the relative energy difference distribution (REDD). The force field developed through AFM significantly improves the REDD when compared with standard MM models, thus improving the convergence of the ab initio FEP calculation. The static dielectric constant ε_s of ice-Ih was studied with PW-91 through ab initio FEP. With a customized force field developed through AFM, we were able to converge ε_s to 80 ± 4 with 3,600 configurations. A similar ab initio FEP calculation with the TIP4P model would require 220 times more configurations to achieve the same accuracy. Our study indicates that the PW-91 functional underestimates ice-Ih ε_s by about 20%.     

Spectroscopic studies on the interaction of cilostazole with iodine and 2,3-dichloro-5,6-dicyanobenzoquinone

Lanthanide sensitized luminescence and chemiluminescence (CL) are of great importance because of the unique spectral properties, such as long lifetime, large Stokes shifts, and narrow emission bands characteristic to lanthanide ions (Ln³⁺). With the fluoroquinolone (FQ) compounds including enoxacin (ENX), norfloxacin (NFLX), lomefloxacin (LMFX), fleroxacin (FLRX), ofloxacin (OFLX), rufloxacin (RFX), gatifloxacin (GFLX) and sparfloxacin (SPFX), the luminescence and CL properties of Tb³⁺–FQ and Eu³⁺–FQ complexes have been investigated in this contribution. Ce⁴⁺–SO₃²⁻ in acidic conditions was taken as the CL system and sensitized CL intensities of Tb³⁺–FQ and Eu³⁺–FQ complexes were determined by flow-injection analysis. The luminescence and CL spectra of Tb³⁺–FQ complexes show characteristic peaks of Tb³⁺ at 490 nm, 545 nm, 585 nm and 620 nm. Complexes of Tb³⁺–ENX, Tb³⁺–NFLX, Tb³⁺–LMFX and Tb³⁺–FLRX display relatively strong emission intensity compared with Tb³⁺–OFLX, Tb³⁺–RFX, Tb³⁺–GFLX and Tb³⁺–SPFX. Quite weak peaks with unique characters of Eu³⁺ at 590 nm and 617 nm appear in the luminescence and CL spectra of Eu³⁺–ENX, but no notable sensitized luminescence and CL of Eu³⁺ could be observed when Eu³⁺ is added into other FQ. The distinct differences on emission intensity of Tb³⁺–FQ and Eu³⁺–FQ might originate from the different energy gap between the triplet levels of FQ and the excited levels of the Ln³⁺. The different sensitized luminescence and CL signals among Tb³⁺–FQ complexes could be attributed to different optical properties and substituents of these FQ compounds. The detailed mechanism involved in the luminescence and CL properties of Tb³⁺–FQ and Eu³⁺–FQ complexes has been investigated by analyzing the luminescence and CL spectra, quantum yields, and theoretical calculation results.     

Synthesis of Cu-mediated nano-sized salbutamol-imprinted polymer and its use for indirect recognition of ultra-trace levels of salbutamol

Cu²⁺-mediated salbutamol-imprinted polymer nanoparticles, synthesized by precipitation polymerization, were mixed with graphite powder and n-eicosane in order to fabricate a modified carbon paste electrode. This electrode was then applied for indirect differential pulse voltammetry determination of salbutamol. In the presence of Cu²⁺ ions, the formed Cu²⁺–salbutamol complex was adsorbed in to the pre-designed cavities of the MIP particles, situated on the electrode surface. Since the electrochemical signal of salbutamol was intrinsically small, the oxidation peak of the participant Cu²⁺, after reduction step, was recorded and used as an indication of salbutamol amount, adsorbed in the electrode. Different variables influencing the sensor performance were studied and the best conditions were chosen for the determination purpose. Correlation between the sensor response to salbutamol and its concentration was linear in the range of 1.0 × 10⁻⁹–5.5 × 10⁻⁸ M. Detection limit was calculated equal to 6.0 × 10⁻¹⁰ M (S/N). Five replicated determination of salbutamol (1 × 10⁻⁸ M) resulted in standard error of 3.28%, meaning a satisfactory precision of the determination method. The prepared sensor was applied for real sample analysis. In order to minimize the interference effect, the synthesized polymer was successfully used as a solid phase sorbent for salbutamol extraction, before analysis of real samples by the developed sensor.     

Ion-beam irradiation effects on polyimide-UV–vis and infrared spectroscopic study

Ion-beam irradiation effects on polyimide, Kapton™, were studied with respect to optical and electronic properties. Stack films of Kapton™ (12.5 μm thick) were irradiated to various ion beams in air or vacuo at room temperature and subjected to ultraviolet–visible (UV–vis) spectroscopy, and change in absorbance and energy gap is discussed. The UV–vis absorption spectrum, which is assigned to the transition of electrons in benzene rings from π to π* orbital, upon He²⁺ (6 MeV/u) irradiation in air, shifted towards longer wavelength direction for all cases, and the shift was more obvious for higher linear energy transfer (LET) ion beams. The energy gap of the transition was estimated, and the H⁺ and He²⁺ ion beams caused little change in the transition energy gap Eg, while the heavier ions such as C⁶⁺ and Si¹⁴⁺ caused more significant decrease. This decrease is assumed to the structural changes around benzene rings, and the infrared spectroscopy revealed breakage in imide groups next to benzene ring in the repeating unit of polyimide.     

Swift heavy ion induced modification in dielectric and microhardness properties of polymer composites

Polymer composites with different concentrations of organometallics (ferric oxalate) dispersed PMMA were prepared. PMMA was synthesized by solution polymerization technique. These films were irradiated with 120 MeV Ni¹⁰⁺ ions in the fluence range 10¹¹-5 × 10¹² ions/cm². The radiation induced modifications in dielectric properties, microhardness, structural changes and surface morphology of polymer composite films have been investigated at different concentrations of filler and ion-fluences. It was observed that electrical conductivity and hardness of the films increase with the concentration of the filler and also with the fluence. The dielectric constant (?) obeys the Universal law given by ?αfⁿ⁻¹. The dielectric constant/loss is observed to change significantly due to irradiation. This suggests that ion beam irradiation promotes the metal to polymer bonding and convert polymeric structure into hydrogen depleted carbon network. This makes the composites more conductive and harder. Surface morphology of the films has been studied using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The average surface roughness is observed to increase after irradiation as revealed by AFM studies. The SEM images show the blisters type of phenomenon on the surface due to ion beam irradiation.     

Graphene oxide amplified electrochemiluminescence of graphitic carbon nitride and its application in ultrasensitive sensing for Cu

Here for the first time, we present a novel electrochemiluminescence (ECL) sensor based on graphitic carbon nitride/graphene oxide (g-C₃N₄/GO) hybrid for the ultrasensitive detection of Cu²⁺, which is a common pollutant in environmental system. The g-C₃N₄/GO shows stable ECL signal in the presence of the self-produced coreactant from oxygen reduction, and the ECL signal could be effectively quenched by Cu²⁺, the possible ECL detection mechanism has been proposed in detail. GO can not only significantly enhance the cathodic ECL signal of g-C₃N₄ (∼3.8 times), but also serve as immobilization platform for g-C₃N₄. After optimization of experimental conditions, the proposed protocol can offer an ultrasensitive, highly selective and recyclable method for the detection of Cu²⁺ with a low detection limit of 1.0 × 10⁻¹¹ M and a wide linear range from 1.0 × 10⁻¹¹ to 1.0 × 10⁻⁷ M. Moreover, the practicability of the ECL sensor in real wastewater samples is also tested, showing that the proposed ECL sensor could be a promising alternative method for the emergency and routine monitoring of Cu²⁺ in real sample.     

Sputtering of bismuth thin films under MeV Cu heavy ion irradiation: Experimental data and inelastic thermal spike model interpretation.

The sputtering of bismuth (Bi/Si) thin films deposited onto silicon substrates and irradiated by swift Cu^q+ heavy ions (q = +4 to +7) was investigated by varying both the ion energy over the 10 to 26‐MeV range and the ion fluence ϕ from 5.1 × 10¹³ cm⁻² to 3.4 × 10¹⁵ cm⁻². The sputtering yields were determined experimentally via the Rutherford backscattering spectrometry technique using a 2‐MeV He⁺ ion beam. The measured sputtering yields versus Cu⁷⁺ ion fluence for a fixed incident energy of 26 MeV exhibit a significant depression at very low ϕ‐values flowed by a steady‐state regime above ~1.6 × 10¹⁴ cm⁻², similarly to those previously pointed out for Bi thin films irradiated by MeV heavy ions. By fixing the incident ion fluence to a mean value of ~2.6 × 10¹⁵ cm⁻² in the upper part of the yield saturation regime, the measured sputtering yield data versus ion energy were found to increase with increasing the electronic stopping power in the Bi target material. Their comparison to theoretical predicted models is discussed. A good agreement is observed between the measured sputtering yields and the predicted ones when considering the contribution of 2 competitive processes of nuclear and electronic energy losses via, respectively, the SRIM simulation code and the inelastic thermal spike model using refined parameters of the ion slowing down with reduced thermophysical proprieties of the Bi thin films.     

Synthesis,crystal structure and properties of a quaternary oxide with a new structure type,BiGaTi4O11

A new quaternary oxide, BiGaTi₄O₁₁ (bismuth gallium tetratitanium undecaoxide), was prepared by heating a mixture of the binary oxides at 1373 K in air. BiGaTi₄O₁₁ melts at 1487 K and prismatic single crystals were obtained from a sample melted at 1523 K and solidified by furnace cooling. The structure of BiGaTi₄O₁₁ was analyzed using single‐crystal X‐ray diffraction to be of a new type that crystallized in the space group Cmcm. A Bi³⁺ site is coordinated by nine O^2? anions, and three oxygen‐coordinated octahedral sites are statistically occupied by Ga³⁺ and Ti⁴⁺ cations. A relative dielectric constant of 46 with a temperature coefficient of 57 ppm K^?1 in the temperature range 297–448 K was measured for a polycrystalline ceramic sample at 150 Hz–1 MHz with a dielectric loss tan δ of less than 0.01. Electrical resistivities measured at 1073 K by alternating‐current impedance spectroscopic and direct‐current methods were 1.16 × 10^?4 and 1.14 × 10^?4 S cm^?1, respectively, which indicates that electrons and/or holes were conduction carriers at high temperature. The optical band gap estimated by the results of diffuse reflectance analysis was 2.9–3.0 eV, while the band gap obtained from the activation energy for electrical conduction was 3.5 eV.     

Electrical behaviour of butyl acrylate/methyl methacrylate copolymer films irradiated with 1.5 MeV electron beam

Electrical conductivity and dielectric parameters of the (BuA/MMA) copolymer films irradiated with 1.5 MeV electron beam (EB) have been studied. The samples were irradiated with different doses of the electron beam: 5, 10, 50, 125 and 200 kGy. The electrical conductivity of the samples was found to decrease as the irradiation dose increases. The temperature dependence of the direct current (dc) conductivity for unirradiated and irradiated samples has been obtained over a temperature range from 293 to 373 K. The activation energy values were calculated for all samples. Moreover, measurements of the dielectric constant, dielectric loss and alternating current (ac) conductivity were performed at a frequency range from 100 Hz to 5 MHz at room temperature. The results indicated that the EB irradiation has formed some traps in the energy gap, which reduce the movement of the charge carriers. Furthermore, a direct proportional relationship between the activation energy and the irradiation dose was estimated in two regions: below and above the glass transition temperature of the polymer. Dipole relaxation was observed in the samples, and the dose effect was found to shift this relaxation towards higher frequencies.     

Determination Co2+ in vitamin B12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H2O2 chemiluminescence reaction

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H₂O₂ has been investigated. It was also found that MDFI/H₂O₂ and t-BDFI/H₂O₂ systems gave strong CL. When Co²⁺ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co²⁺. The linear ranges are 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for MDFI/H₂O₂ system and 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for t-BDFI/H₂O₂ system, and the corresponding detection limits are 1.2 × 10⁻⁹ mol/L and 1.1 × 10⁻⁹ mol/L, respectively. The method was applied to the determination of Co²⁺ in vitamin B₁₂ injection. Furthermore, the CL mechanism was also discussed.     

Multiplex sensor for detection of different metal ions based on on–off of fluorescent gold nanoclusters

In this study, a multiplex fluorescence sensor for successive detection of Fe³⁺, Cu²⁺ and Hg²⁺ ions based on “on–off” of fluorescence of a single type of gold nanoclusters (Au NCs) is described. Any of the Fe³⁺, Cu²⁺ and Hg²⁺ ions can cause quenching fluorescence of Au NCs, which established a sensitive sensor for detection of these ions respectively. With the introduction of ethylene diamine tetraacetic acid (EDTA) to the system of Au NCs and metal ions, a restoration of fluorescence may be found with the exception of Hg²⁺. A highly selective detection of Hg²⁺ ion is, thus, achieved by masking Fe³⁺ and Cu²⁺. On the other hand, the masking of Fe³⁺ and Cu²⁺ leads to the enhancement of fluorescence of Au NCs, which in turn provides an approach for successive determination of Fe³⁺ and Cu²⁺ based on “on–off” of fluorescence of Au NCs. Moreover, this assay was applied to the successful detection of Fe³⁺, Cu²⁺ and Hg²⁺ in fish, a good linear relationship was found between these metal ions and the degree of quenched fluorescent intensity. The dynamic ranges of Hg²⁺, Fe³⁺ and Cu²⁺ were 1.96 × 10⁻¹⁰–1.01 × 10⁻⁹, 1.28 × 10⁻⁷–1.27 × 10⁻⁶ and 1.2 × 10⁻⁷–1.2 × 10⁻⁶ M with high sensitivity (the limit of detection of Fe³⁺ 2.0 × 10⁻⁸ M, Cu²⁺ 1.9 × 10⁻⁸ M and Hg²⁺ 2 × 10⁻¹⁰ M). These results indicate that the assay is suitable for sensitive detection of these metal ions even under the coexistence, which can not only determine all three kinds of metal ions successively but also of detecting any or several kinds of metal ions.     

ESR study for ion beam induced phenomena in poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP)

Trapped radicals induced in poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) were observed by X-band electron spin resonance (ESR) spectroscopy at room temperature (RT) under atmospheric field after an irradiation with various kinds of high energy ion beams (6 MeV/u). The irradiation was carried out to a stacked FEP films under vacuum (<4E?4 Pa) at RT with various fluences from 1.0×10⁹ to 1.0×10¹¹ ions/cm². All ESR spectra indicated an existence of peroxy radicals in each of the FEP films without any relation to a kind of ion and a penetration depth. Obtained depth profiles of radical concentrations induced with each ion beam almost correspond to those of stopping power. The trapped radical concentrations were strongly dependent on stopping power. It was found that G-value of trapped radicals by ion beam irradiation was decreased with increasing a stopping power, and was less than the case of gamma-rays irradiation.     

Fluoride ions at the Cu–fluoropolymer interface

Nanometer thick films of sputtered and evaporated Cu were deposited on the surfaces of the fluoropolymers poly(tetrafluoroethylene) (PTFE), poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) and poly(tetrafluoroethylene‐co‐perfluoropropyl vinyl ether) (PFA) and studied by both angle‐resolved XPS at takeoff angles of 10°, 45° and 80° and in situ argon ion etching. Higher yields of the fluoride ion to fluoropolymer ratio were detected for sputtered than evaporated Cu. PFA and FEP show enhanced interaction with sputtered Cu to produce fluoride ions relative to the more polycrystalline PTFE. At intermediate depths (takeoff angle of 45°), PFA and FEP exhibit the strongest fluoride F 1s signals compared with the fluoropolymer peaks. The amount of fluoride ion detected reaches a maximum after brief Ar ion etching and then decreases with prolonged etching. Compared with untreated fluoropolymers, improved adhesion of evaporated Cu was observed on the fluoropolymer surfaces that were argon ion etched to expose fluoride ions. Copyright © 2013 John Wiley & Sons, Ltd.