IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO₂ laser ablation of films of poly(methyl methacrylate), PMMA, with average M_W 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF₂ substrates were irradiated with a pulsed CO₂ laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm². Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high M_W polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer M_W and filaments are observed to be ejected out of the irradiated volume in the samples made with high M_W polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.     

Examination of the influence of molecular weight on polymer laser ablation: polystyrene at 248 nm

Following previous studies on the influence of the polymer molecular weight (M_W) on the ablation of poly(methyl methacrylate) (PMMA) at 248 nm, this work extends the examination to the ablation of polystyrene (PS) at 248 nm. The ablation threshold and the etching rates are found to be nearly independent of M_W. Optical microscopy demonstrates an excellent crater morphology, few small bubbles are formed on the surface of the low M_W. Examination of the formation kinetics of products in the irradiation of samples doped with the photoreactive iodophenanthrene demonstrates that high temperatures develop upon irradiation, suggesting that thermal mechanism dominates in the ablation of PS at 248 nm. In similarity to the etching rates, the attained temperatures are largely independent of the PS M_W. The factors for the weak dependence of the process on PS M_W are discussed.     

Suppress polystyrene thin film dewetting by modifying substrate surface with aminopropyltriethoxysilane

Aminofunctional organosilanes, such as 3-aminopropyltriethoxysilane (APTES), have been widely utilized as adhesion promoters, and have also been found to have the ability to prevent dewetting of polymer thin films from substrates. The APTES molecule contains an active terminal amino group that can hydrogen bond with the multiple hydroxylated head groups in itself and hydroxyl groups on a substrate, thus forming cyclic structures and a complex loose network at ambient conditions. Upon heating, the hydrogen bond can be broken, allowing more silanol groups to condense with each other and form siloxane linkages, hence tightening the three-dimensional network. When a polymer thin film is in contact with the APTES layer during the thermal process, the polymer chains can diffuse/penetrate into the APTES network while the network is being tightened by the additional crosslinking. The penetrated and subsequently anchored chains could help to stabilize the thin film on the substrate. This hypothesis was verified by dewetting studies of thin films of polystyrene (PS), having molecular weights above and below the entanglement molecular weight (M_e), from APTES and control surfaces when the systems were subjected to various treatments. Dewetting suppression was observed for PS/APTES that was thermally treated at ∼80 °C or 120 °C prior to the annealing of the thin film at higher temperatures. Much stronger suppression was noticed for PS having a molecular weight higher than M_e. When PS thin films were deposited onto a precured APTES network, no dewetting suppression was observed.     

Computational and experimental study of the cluster size distribution in MAPLE

A combined experimental and computational study is performed to investigate the origin and characteristics of the surface features observed in SEM images of thin polymer films deposited in matrix-assisted pulsed laser evaporation (MAPLE). Analysis of high-resolution SEM images of surface morphologies of the films deposited at different fluences reveals that the mass distributions of the surface features can be well described by a power-law, Y(N) ∝ N^−t, with exponent −t ≈ −1.6. Molecular dynamic simulations of the MAPLE process predict a similar size distribution for large clusters observed in the ablation plume. A weak dependence of the cluster size distributions on fluence and target composition suggests that the power-law cluster size distribution may be a general characteristic of the ablation plume generated as a result of an explosive decomposition of a target region overheated above the limit of its thermodynamic stability. Based on the simulation results, we suggest that the ejection of large matrix-polymer clusters, followed by evaporation of the volatile matrix, is responsible for the formation of the surface features observed in the polymer films deposited in MAPLE experiments.     

Polymer Surface Functionalization Using Plasma,Ultraviolet and Synchrotron Radiation

Polyurethane (PU) and polystyrene (PS) films were functionalized by ultraviolet (UV) or selective synchrotron radiations (SR) in the presence of reactive gases. The UV-PU results were compared with lowpressure plasma treatments of the same films. Oxygen or acrylic acid vapours (AA) were used as reactive gases. X-ray photoelectron spectroscopy measurements of UV modified films in the presence of oxygen or AA matched the RF-plasma treatments results. It is shown that COO and C=O functional groups were incorporated at the polymer surface efficiently with both methodologies. In addition, near-edge X-ray absorption fine structure showed that a thin film of poly(acrylic acid) is formed over the PU and PS films during the UV irradiation in the presence of AA vapours. These results resemble previous AA low-power plasma treatments. PU and PS films were also selectively functionalized by SR using oxygen as reactive gas. Surface concentrations of COO and C=O functional groups were enhanced by C_1s → σ* _C–C excitation after irradiation and oxygen introduction. This efficient surface functionalization was clearly observed in PS films which do not have CO and COO groups in their molecular structure. Excitations involving transitions to π* orbital (π*_C=C, π*_C=O) led to much lower functionalization efficiency. The SR results can be explained by taking into account previous photon stimulated ion desorption studies of polymers. SR results may open new ways to functionalize polymer surfaces selectively and efficiently.     

Nanosecond and femtosecond UV laser ablation of polymers: Influence of molecular weight

We examine the nanosecond and femtosecond UV laser ablation of poly(methyl methacrylate) (PMMA) as a function of molecular weight (M_w). For laser ablation with nanosecond laser pulses, at the excimer wavelengths 248 nm and 193 nm, we show that high temperatures develop; yet the dynamics of material ejection differs depending on polymer M_w. The results on the nanosecond ablation of polymers are accounted within the framework of bulk photothermal model and the results of molecular dynamics simulations. Turning next to the 248 nm ablation with 500 fs laser pulses, the ablation threshold and etching rates are also found to be dependent on polymer M_w. In addition, ablation results in morphological changes of the remaining substrate. Plausible mechanisms are advanced.     

Similarity rules of magnetic minor hysteresis loops in Fe and Ni metals

We have studied similarity rules of quasistatic minor hysteresis loops for Fe and Ni single crystals in the wide temperature range from 10 to 600 K. Two similarity rules of M_R*/M_a*∼3/4 and W_R*/W_F*∼1/6, were found in a medium field range where irreversible movement of Bloch walls plays a crucial role for magnetization; M_a*, M_R*, W_F*, and W_R* are magnetization, remanence, hysteresis loss, and remanence work of a minor hysteresis loop. The similarity rules hold true, being almost independent of kinds of ferromagnets, applied stress, and temperature. The origin was discussed from the viewpoint of pinning effects due to dislocations as well as eddy current effects which become predominant at low temperatures for samples with low dislocation density.     

Planar quarter wave stacks prepared from chalcogenide Ge-Se and polymer polystyrene thin films

Planar quarter wave stacks based on amorphous chalcogenide Ge-Se alternating with polymer polystyrene (PS) thin films are reported as Bragg reflectors for near-infrared region. Chalcogenide films were prepared using a thermal evaporation (TE) while polymer films were deposited using a spin-coating technique. The film thicknesses, d∼165 nm for Ge₂₅Se₇₅ (n=2.35) and d∼250 nm for polymer film (n=1.53), were calculated to center the reflection band round 1550 nm, whose wavelengths are used in telecommunication. Optical properties of prepared multilayer stacks were determined in the range 400-2200 nm using spectral ellipsometry, optical transmission and reflection measurements. Total reflection for normal incidence of unpolarized light was observed from 1530 to 1740 nm for 8 Ge-Se+7 PS thin film stacks prepared on silicon wafer. In addition to total reflection of light with normal incidence, the omnidirectional total reflection of TE-polarized light from 8 Ge-Se+7 PS thin film stacks was observed. Reflection band maxima shifted with varying incident angles, i.e., 1420-1680 nm for 45° deflection from the normal and 1300-1630 nm for 70° deflection from the normal.     

Effective biaxial modulus and strain energy density of ideally (h k l)-fiber-textured cubic polycrystalline films

The effective biaxial modulus (M_eff) and strain energy density (W) of cubic polycrystalline films with ideally (h k l) fiber textures are estimated using Vook-Witt (VW) grain interaction model and the data are compared with those derived from Voigt, Reuss and Voigt-Reuss-Hill (VRH) models. Numerical results show that the VW average of M_eff for ideally (1 0 0)- or (1 1 1)-fiber-textured films is identical to the VRH average of M_eff. For (1 1 0) and (1 1 2) planes, however, the VW average of M_eff for (1 1 0)-fiber-textured film is larger than that of (1 1 2)-fiber-textured film when the Zener anisotropic factor (A_R) is not equal to 1. Furthermore, M_eff and W exhibit incremental tendencies with the increase of the orientation factor (Γ_h k l) for the [h k l] axis when A_R > 1, implying that M_eff and W have the minimums on the (1 0 0) plane. Reversely, M_eff and W decrease with the increasing Γ_h k l when A_R < 1. This means that M_eff and W on (1 1 1) plane have the minimums.     

Change in optical path length of saturable absorbing dye-doped polymer films under laser irradiation

The cause of the change in the optical path lengthΔ(nd) of the saturable absorbing dye-doped polymer films under laser irradiation is investigated using polyvinyl alcohol and gelatin films doped with erythrosin B. The temperature rise of the dye-doped films, the changes in optical path length, film thickness, the refractive index and the optical density of the dye-doped films are measured under laser irradiation. The thermal expansion due to the temperature rise of the dye-doped films caused by the irradiation has greater effect on theΔ(nd) than the fading of dye molecules due to the irradiation of laser beams.     

How to compare the SU(5) value of sin2θw with experiments?

We establish the relation between κsin²θ_w to be found from neutral-current experiments and sin²θ_w(Q) for Q=M_W predicted by grand unified theories. We then calculate sin²θ_W(M_W) in the minimal SU(5) model taking the M_W as well as M_x threshold effects into account. We find that these two threshold effects on sin²θ_W(M_W) cancel with each other and sin²θ_W(M_W)=0.211± 0.005.     

Complete magnetizing field relating with magnetization reversal dynamics

We report the experimental finding that a complete magnetizing field H_M exists in magnetization reversal dynamics of ferromagnetic thin films, which is much larger than the apparent magnetic saturation field measured from the major hysteresis loop. Magnetization reversal dynamics contrastingly changes from nucleation dominated to wall-motion dominated according to an initial magnetization state magnetized by a field below H_M, whereas it is basically unchanged when the field is larger than H_M. The complete magnetizing field is found to be 1.5–2.0 times larger than the apparent magnetic saturation field and 6–10 times smaller than the anisotropy field in Co/Pd multilayer thin films.     

Concurrent concentration declines in groundwater-dissolved radon,methane and ethane precursory to 2011 MW 5.0 Chimei earthquake

Radon volatilization mechanism into the gas phase was hypothesized to explain the anomalous declines in groundwater radon precursory to three major earthquakes – (1) 2003 M_W = 6.8 Chengkung, (2) 2006 M_W = 6.1 Taitung, and (3) 2008 M_W = 5.4 Antung in Taiwan. The epicenters were located 24 km, 52 km, and 13 km from the Antung radon-monitoring well D1, respectively. To verify the mechanism of in situ volatilization, we monitored groundwater-dissolved ethane in addition to radon and methane at well D1 in the Antung hot spring since November 30, 2010. The mechanism of in situ radon volatilization has been corroborated by the simultaneous concentration declines in groundwater-dissolved radon, methane, and ethane precursory to the 2011 M_W 5.0 Chimei earthquake. The epicenter was located 32 km from the Antung radon-monitoring well D1. Observations at the Antung hot spring also suggest that radon is the best-choice tracer among the groundwater-dissolved gases for strain changes in the crust preceding an earthquake. On the southern segment of the Chihshang fault, the observed radon minima decrease as the earthquake magnitude increases.     

On the correlation between droplet volume and irradiation conditions in the laser forward transfer of liquids

The analysis of the morphology of droplets printed through laser-induced forward transfer (LIFT) of liquid films shows that: (i)?the droplet volume is linearly related with the energy of the laser pulse that originated it, (ii)?the liquid ejection process is activated by an energy density threshold?F ₀, and (iii)?the droplet volume can be correlated with a dimensional parameter of the laser beam through an oversimple model that states that the amount of printed liquid equals the liquid contained in the cylindrical portion of an irradiated film whose base corresponds to the cross-sectional area of the beam with energy density higher than?F ₀. Although these issues seem to describe correctly the LIFT process, some problematic instances arise from them. Thus, the linear relation between droplet volume and laser pulse energy seems to be inconsistent with the existence of the threshold?F ₀. On the other hand, the compatibility between the model and the aforementioned linear relation requires to be explained. Finally, the model is based on the idea that transfer takes place in a way analogous to the LIFT of solid films, but time-resolved imaging studies have demonstrated that liquid ejection follows a dynamics which seems quite unsuited with that idea. In this work previous results are re-analyzed and new experiments are performed in an attempt to clarify these questions. It is then shown that the inconsistencies pointed out are only apparent, and that the validity of the model is limited to irradiation conditions where the beam dimensions are significantly larger than the thickness of the liquid film. Furthermore, an explanation is provided for the dependence of the success and failure of the model on those irradiation conditions in terms of the diverse liquid ejection dynamics taking place.     

Laser-induced periodic surface structures on polymers for formation of gold nanowires and activation of human cells

Frequently observed coherent structures in laser-surface processing are ripples, also denoted as laser-induced periodic surface structures (LIPSS). For polyethylene terephthalate (PET) and polystyrene (PS), LIPSS can be induced by irradiation with linearly polarized ns-pulsed UV laser light. Under an angle of incidence of θ, their lateral period is close to the laser wavelength λ divided by (n _eff ? sinθ). Here, n _eff is the effective refractive index which is 1.32 and 1.23 for PET and PS, respectively. We describe potential applications of LIPSS for alignment and activation of human cells cultivated on polymer substrates, as well as for formation of separated gold nanowires which show pronounced surface plasmon resonances, e.g., at 775 nm for PET.     

Synthesis and physical properties of negative thermal expansion materials Zr1−xMxW2O8−y (M=Sc, In, Y) substituted for Zr(IV) sites by M(III) ions

Zr_1−xM_xW₂O_8−y (M=Sc, In and Y) solid solutions substituted up to x=0.04 for Zr(IV) sites by M(III) ions were synthesized by a solid-state reaction. X-ray diffraction experiments from 90 to 560 K revealed that all solid solutions had a cubic crystal structure and showed negative thermal expansion coefficients. The lattice parameters of Zr_1−xM_xW₂O_8−y were smaller than that of ZrW₂O₈ probably due to oxygen defects, though the ionic radii of substituted M³⁺ ions were larger than that of Zr⁴⁺. Order-disorder phase transition temperatures of the substituted samples drastically decreased in the order of Y, In and Sc compared to the percolation theory, and decreased with increasing M content.     

The properties of free polymer surfaces and their influence on the glass transition temperature of thin polystyrene films

We present a detailed study of free polymer surfaces and their effects on the measured glass transition temperature (T_g) of thin polystyrene (PS) films. Direct measurements of the near-surface properties of PS films are made by monitoring the embedding of 10 and 20 nm diameter gold spheres into the surface of spin-cast PS films. At a temperature T = 378K( > T_g), the embedding of the spheres is driven by geometrical considerations arising from the wetting of the gold spheres by the PS. At temperatures below T_g ( 363K < T < 370K), both sets of spheres embed 3-4 nm into the PS films and stop. These studies suggest that a liquid-like surface layer exists in glassy PS films and also provide an estimate for the lower bound of the thickness of this layer of 3-4 nm. This qualitative idea is supported by a series of calculations based upon a previously developed theoretical model for the indentation of nanoscale spheres into linear viscoelastic materials. Comparing data with simulations shows that this surface layer has properties similar to those of a bulk sample of PS having a temperature of 374 K. Ellipsometric measurements of the T_g are also performed on thin spin-cast PS films with thicknesses in the range 8nm < h < 290nm. Measurements are performed on thin PS films that have been capped by thermally evaporating 5 nm thick metal (Au and Al) capping layers on top of the polymer. The measured T_g values (as well as polymer metal interface structure) in such samples depend on the metal used as the capping layer, and cast doubt on the general validity of using evaporative deposition to cover the free surface. We also prepared films that were capped by a new non-evaporative procedure. These films were shown to have a T_g that is the same as that of bulk PS (370±1 K) for all film thicknesses measured (> 7 nm). The subsequent removal of the metal layer from these films was shown to restore a thickness-dependent T_g in these samples that was essentially the same as that observed for uncapped PS films. An estimate of the thickness of the liquid-like surface layer was also extracted from the ellipsometry measurements and was found to be 5±1 nm. The combined ellipsometry and embedding studies provide strong evidence for the existence of a liquid-like surface layer in thin glassy PS films. They show that the presence of the free surface is an important parameter in determining the existence of T_g reductions in thin PS films.     

Molecular-weight dependence of the glass transition temperature of freely-standing poly(methyl methacrylate) films

We have used transmission ellipsometry to measure the glass transition temperature, T_g, of freely-standing films of atactic and syndiotactic poly(methyl methacrylate) (PMMA). We have prepared films with different molecular weights, MW, (159×10³ < M _w < 1.3×10⁶) and film thicknesses, h, ( 30nm < h < 200 nm). For the high-MW ( M _w > 509×10³) atactic PMMA films, we find that T_g decreases linearly with decreasing h, which is qualitatively similar to previous results obtained for high-MW freely-standing polystyrene (PS) films. However, the overall magnitude of the T_g reduction is much less (by roughly a factor of three) for the high-MW freely-standing PMMA films than for freely-standing PS films of comparable MW and h. The observed differences between the freely-standing PMMA and PS film data suggest that differences in chemical structure determine the magnitude of the T_g reduction and we discuss the possible origins of these differences. Our analysis of the MW-dependence of the T_g reductions suggests that the mechanism responsible for the MW-dependent T_g reductions observed in the high-MW freely-standing films is different than that responsible for the MW-independent T_g reductions observed in the low-MW freely-standing and supported films.     

Impact parameter dependence of the probability for removal of the 2s and 2p atomic electrons by nuclei

The probability W(x) of inner shell ionization by nuclei as a function of the impact parameter x is expressed through the ionization matrix element M_if. Values of W(x) for removal of the 2s and 2p electrons are calculated with the first Born M_if and compared with the SCA result.     

Studies on radiation effects of PTFE. I. Changes in crystallizing behavior and number average molecular weight of PTFE irradiated at different temperatures

The present work deals with changes in the number average molecular weight (M _n) of PTFE irradiated at different temperatures. A decrease in M _n was observed and attributed to the scission of polymer chains. On the other hand, it was also observed that M _n decreased to a minimum value with increasing irradiation dose and then increased; the doses at which the minimum value of M _n occurs are temperature dependent. The increase is explained as being due to crosslinking reactions occurring during the irradiation of PTFE.