Laser isotope separation of tritium using CF3CTBrF/CF3CHBrF

A new working molecule 2-bromo-1,1,1,2-tetrafluoroethane is reported for laser isotope separation of tritium. The multiphoton dissociation rate of CF₃CTBrF is studied as a function of irradiation wavenumber, using a CO₂ or NH₃ laser. In a tightly focused irradiation geometry where the dissociation saturates both for CF₃CTBrF and CF₃CHBrF, their threshold fluences of dissociation and the geometrically biased selectivity are measured near the maximum of the dissociation rate of CF₃CTBrF. When the irradiation geometry is optimized, a high selectivity exceeding 2700 is obtained.     

Theoretical and experimental investigations on the deposition rate and processes of parallel incident laser-induced CVD

A theoretical analysis of and experimental observations on a parallel incident laser-induced deposition rate are reported. Our theory predicts that the maximum deposition rate depends on the photo-traveling length, the scattering cross section of the reactant gases and their partial pressure. This result is applied to SiO₂ deposition using monosilane and nitrous oxide for reactant gases, and is compared with experimental results. We show that the deposition rate of SiO₂ films as a function of the incident light power and the partial pressure of reactant gases predicted by the present theory well explains our experimental results. A supply-limitation phenomenon of the reactant gases and a method of estimating deposition efficiencies are also discussed.     

Experimental study of cw carbon monoxide flame chemical laser of the CS2/O2/CO2 type

The performance of a continuous-wave (cw) CO flame chemical laser (FCL) of the CS₂/O₂/CO₂ type is presented. The laser gives up to 0.7 W cw output power on a number ofP _v (J) lines corresponding to 1110, ..., 76 vibrational bands of CO molecule. The measured values of chemical efficiency based on the reaction O+CSCO^*(v)+S and the specific power are 0.1% and 0.7J/g, respectively. The spectral composition of the CO FCL of the CS₂/O₂/CO₂ type shows lasing in the region from 5.194 to 5.573 m. All experimental measurements are conducted with a nondispersive optical cavity.     

CO2 laser ablative etching of polyethylene terephthalate

Films of polyethylene terephthalate (PET) can be successfully etched with 9 m radiation from a pulsed TEA CO₂ laser. The relationship between etch depth and fluence is broadly similar to that observed for excimer laser etching but with a less well-defined threshold. Time-resolved photoacoustic measurements of stress waves generated in the interaction show that at a fluence of 1.8 J cm^–2 ablation occurs 100–200 ns after the start of the laser pulse, a time which is consistent with the rate of thermal decomposition of PET. The volatile products of ablation are carbon monoxide, carbon dioxide, methane, ethyne, ethene, benzene, ethanal, and small quantities of other products. For fluences close to and appreciably above the threshold the ablated material consists predominantly of involatile species of relatively high molecular weight, whereas at higher fluences substantial fragmentation of the polymer to small molecules occurs.School of Chemistry     

Experimental study of minimum ignition energy of lean H2-N2O mixtures

Ignition energies for short duration (<50 ns) spark discharges were measured for undiluted and nitrogen-diluted H₂-N₂O mixtures of equivalence ratios ? = 0.15 and 0.2, dilution of 0% and 20% N₂, and initial pressures of 15–25 kPa. The ignition events were analyzed using statistical tools and the probability of ignition versus spark energy density (spark energy divided by the spark length) was obtained. The simple cylindrical ignition kernel model was compared against the results from the present study. Initial pressure has a significant effect on the width of the probability distribution, ranging from a broad (P = 15 kPa) to a narrow (P = 25 kPa) probability distribution indicating that the statistical variation of median spark energy density increases as initial pressure of the mixture decreases. A change in the equivalence ratio from 0.15 to 0.2 had a small effect on the median spark energy density. The addition of 20% N₂ dilution caused a significant increase in the median spark energy density when compared to no dilution. The extrapolation of the present results to atmospheric pressure, stoichiometric H₂-N₂O indicates that the electrostatic discharge ignition hazards are comparable to or greater than H₂-O₂ mixtures.     

An experimental study of self-focusing and self-defocusing of a TEA CO2 laser pulse in CDF3

We observed self-focusing and self-defocusing of a TEA CO₂ laser pulse in CDF₃ vapor under different conditions. The experimental parameters we varied are the pressure inside the interaction cell, the frequency of the laser, the energy and the temporal length of the pulse. We have shown that it is possible to pass from self-focusing to self-defocusing by only increasing the intensity of the laser pulse. We propose a physical model that can explain these experimental results. This model is different from that used to explain the selffocusing of a CO₂ laser in SF₆.     

Laser isotope separation of carbon by multiple IR photon and subsequent UV excitation of CF3I molecules

A new approach to laser isotope separation is considered. It is based on collisionless multiple photon ir laser excitation and subsequent uv laser dissociation of vibrationally excited molecules. TEA CO₂ and excimer XeF, XeCl lasers are used for ir excitation and uv dissociation, respectively. The products of photolysis (C₂F₆) are enriched with¹²C.     

Laser-induced chemistry in silane-hexafluoroacetone mixtures for production of novel Si/C/F/O and C/F/O materials

Chemical reactions induced by CO₂-laser radiation in mixtures of silane and hexafluoroacetone afford various gaseous silicon- and carbon-containing compounds and result in deposition of microstructures of carbon, C/F/O and Si/C/O/F materials. These products are suggested to be formed by a variety of exothermic reactions initiated through SiH₄-photosensitized decomposition of hexafluoroacetone. Silane is shown to be a very potent reagent for the reduction of C-F bonds.     

CO2-laser-induced breakdown in mono- and diatomic gases

Several monoatomic and homonuclear diatomic gases absorb energy from a focused CO₂-laser photon field. It has been established that the pressure threshold for the energy absorption correlates qualitatively with the known ionization potentials of those gases. The simplified phenomenological theory of the CO₂-laser-induced dielectric breakdown of gases is invoked to explain this phenomenon. In the H₂–D₂ system, the formation of HD is observed under these conditions. The examination of the reaction yields for HD formation demonstrates that the system studied does not reach equilibrium under our experimental conditions. Considerations regarding kinetics of primary processes reveal that ionic species, created originally via an inverse bremsstrahlung mechanism, are converted into atomic transients in fast ionic association processes. The latter species initiate chain reactions with surrounding molecules of substrates leading to the formation of HD. Simple kinetic analysis based on a non-steady-state assumption permitted the derivation of an expression for the yield of HD formation. This equation was fitted to the experimental data assuming that the temperature of the reaction rises with an increase of the amount of D₂ in the mixture. Some other aspects regarding the behavior of this system in a focused CO₂ laser beam are also discussed.U.S. Department of Energy Document No. DE-AS02-76ER03416-37     

CO2-laser isotope separation of tritium with pentafluoroethane-T (C2TF5)

Isotope separation of tritium by CO₂ laser-induced multiphoton dissociation (MPD) of C₂TF₅ is reported for the first time. The MPD spectrum obtained for C₂TF₅ comprised a broad peak at about 940 cm^–1 where C₂HF₅ was nearly transparent. The unimolecular dissociation of C₂TF₅ was induced with much lower laser fluence than that for CTF₃, another working molecule we proposed for laser isotope separation of tritium. The mechanisms and kinetics of the dissociation of C₂TF₅ and C₂HF₅ were investigated under various experimental conditions: laser frequency, pulse energy, pulse duration, tritium concentration, sample pressure, buffer gas pressure and irradiation geometry. Single-step separation factors exceeding 500 were achieved with the most efficientP(20) line in 00^o–10^o0 transition at 944.2 cm^–1.     

Production of highly concentrated 13C by continuous two-stage IRMPD. CBr2F2/HI,CCl2F2/HI,and CBrClF2/HI mixtures

Difluoromethane CH₂F₂ containing 90–98% ¹³C was obtained in the selective IRMPD of mixtures of CBr₂F₂/HI, CCl₂F₂/HI, and CBrClF₂/HI. In CBr₂F₂/HI mixtures, the intermediate product CHBrF₂ resulting from the reaction between the initial decomposition fragment CBrF₂ and HI underwent secondary selective IRMPD to form highly ¹³C-enriched CH₂F₂ in continuous laser irradiation. The intermediate product in the mixtures of CCl₂F₂/HI and CBrClF₂/HI was found to be CHClF₂, but no significant secondary photodecomposition in CBrClF₂/HI mixtures occurred owing to the low absorption cross section of CHClF₂ at the adopted laser frequencies and fluences. The observed decomposition probabilities and selectivities under different conditions with respect to laser frequency, fluence, and partial pressures of halogenated difluoromethanes and HI suggest that CBr₂F₂ is one of the better candidates for practical ¹³C separation by IRMPD.     

Tritium isotope separation by CO2-laser irradiation at low temperatures

Tritium isotope separation by CO₂-laser induced multiphoton dissociation of CTF₃ is investigated. For the optimization of the performance of this working substance, trifluoromethane, the conditions to yield high-selectivity at high-operating pressure and low-critical fluence for complete dissociation are studied using our deconvolution procedure. The irradiation conditions are varied over the following ranges; wavenumber: 1052–1087 cm^–1, gas temperature: 25°C to –78°C, CHF₃ pressure: 5–205 Torr. The selectivities exceeding 10⁴ are observed for 85–205 Torr CHF₃ at –78°C by the irradiation at 1057 cm^–1.     

XeCl laser ablation of polyetheretherketone

Ablation of polyetheretherketone (PEEK), a high temperature thermoplastic, by XeCl laser radiation occurs at fluences in excess of 0.07±0.01 J cm^–2. The volatile products of ablation are CO and C₂H₂ with smaller quantities of CH₄, C₄H₂, C₆H₆ and other C₃ and C₄ hydrocarbons. At fluences close to the threshold ablation produces involatile material of relatively high molecular weight but at high fluences extensive disruption of the PEEK structure occurs with conversion of all of the oxygen in the polymer to carbon monoxide.     

Excitation of aliphatic tertiary amines by electrical discharge

Trimethylamine and triethylamine are shown to luminesce at their wavelengths of fluorescence when excited by electrical discharge. When excited at low pressures or at high frequencies, a longer wavelength emission is observed at 380 nm. This emission, rather than being due to excimers which are known to exist for some tertiary aliphatic amines, is shown to be due to emission from a decomposition product. Lasing using electrical discharge pumping was attempted, but yielded negative results due to the rapid decomposition. Optical pumping might be successful however, and produce a tunable gas-phase ultraviolet laser     

Investigations of multiphoton selective dissociation of (CH3)2O in the field of a pulsed CO2 laser

Experimental investigations of multiphoton selective dissociation of (CH₃)₂O induced by a pulsed CO₂ laser have been conducted. Separation of H, C, and O isotopes was performed in enriched mixtures and in samples with the natural abundance. The following coefficients of selectivity have been obtained:K _D/K_H=4.0,K ₁₃/K₁₂=1.7, andK ₁₈/K₁₆≧1.6. We studied the dependences of the selectivity coefficient on ether pressure, on the laser energy and frequency as well as the influence of secondary chemical reactions on the dissociation selectivity. Estimations made by using the RRKM theory have indicated that ether molecules that decompose have an average excitation energy above the dissociation threshold of ∼1.5 kcal/mole.     

Dual excimer and CO2 laser etching studies of polyethylene terephthalate

Polyethylene terephthalate (PET) films preheated with a pulsed CO₂ laser have been ablatively etched with an XeCl laser. The observed reduction in ablation threshold, from 170 to 140 mJ cm^–2, is consistent with a thermal mechanism for XeCl laser ablation of PET. Transient changes in the UV absorption coefficient of PET caused by heating with pulsed CO₂ laser radiation have also been studied and a significant increase in absorption observed at 308 nm. Permanent changes in the ultraviolet absorption of PET following exposure to low fluence XeCl laser radiation are also reported.     

13C-selective two-stage IRMPD of mixtures of CHClF2 and HI

The ¹³C-selective infrared multiple-photon decomposition (IRMPD) of mixtures of CHClF₂ and HI was examined in collimated and focused beam geometries using a CO₂TEA laser. The carbon-containing products were CH₂F₂ and CHF₂I. The former product showed remarkably high ¹³C atom concentrations beyond 95% under selected experimental conditions, while the latter contained 25% or less. The observed results can be explained satisfactorily in terms of the consecutive two-stage IRMPD process occurring in a single irradiation procedure, where the first-stage IRMPD of natural CHClF₂ produces ¹³C-enriched CHF₂I via the insertion of the initial decomposition fragment CF₂ into HI, and the second stage is the subsequent ¹³C-selective IRMPD of the CHF₂I to form a CHF₂ radical and an I atom. The CHF₂ radical reacts with HI to form CH₂F₂. Decomposition probabilities of ¹²CHClF₂ and ¹³CHClF₂ were measured as a function of laser fluence to optimize enrichment conditions. Furthermore, partial decomposition probabilities or relative production yields were measured as functions of laser line, pressure of HI, and pressure of CHClF₂. Both stages showed high ¹³C selectivities in the irradiation with the laser radiation around 1040 cm^–1 and at fluences below 4 J cm^–2. This mixture is one of the most promising chemical systems for the production of highly enriched ¹³C.     

Model for laser-induced thermal degradation and ablation of polymers

Ablation of organic polymers is described on the basis of photothermal bond breaking within the bulk material. Here, we assume a first-order chemical reaction, which can be described by an Arrhenius law. Ablation starts when the density of broken bonds at the surface reaches a certain critical value. In order to understand the ablation behavior near the threshold fluence, φ_th, non-stationary regimes must be considered. The present treatment reveals several qualitative differences with respect to models that treat ablation as a surface process: (i) Ablation starts sharply with a front velocity that has its maximum value just after the onset. (ii) The transition to the quasi-stationary ablation regime is faster. (iii) Near threshold, the ablated depth h has a square-root dependence on laser fluence, i.e., h∝(φ-φ_th)^1/2. The ablation velocity is very high even near φ_th. (iv) With φ≈φ_th ablation starts well after the laser pulse. (v) The depletion of species is responsible for the Arrhenius tail observed with fluences φ≤φ_th. (vi) Residual modification of material has maximum near the threshold. (vii) Stationary regimes of ablation demonstrate change of effective activation energy with laser intensity. The model calculations are applied to Polyimide (Kapton^TM H). Here, differences in single-pulse ablated depth determined from mass loss and profilometry should be about 10 nm. Received: 16 February 1999 / Accepted: 18 February 1999 / Published online: 28 April 1999     

Carbonaceous phases by IR laser-induced decomposition of 3-butyn-2-one

2 laser radiation in the gas phase results in the deposition of carbonaceous films composed of a graphitic and monohydrogenated carbon, in which H is dominantly bonded to sp³ sites. The films incorporate oxygen in the topmost layers. The technique is suitable for the preparation of thin C-based films at low substrate temperatures. Received: 23 July 1997/Accepted: 18 November 1997     

First-stage enrichment in CO2-laser-induced13C separation by a two-stage IRMPD process: IRMPD of CHClF2/Br2 mixtures

We have been studying the practical CO₂-laser-induced¹³C separation by a two-stage IRMPD process. The IRMPD of natural CHClF₂ in the presence of Br₂ mainly produced CBr₂F₂, which was found to be highly enriched with¹³C. The yield and¹³C-atom fraction of CBr₂F₂ were examined as functions of pulse number, laser line, laser fluence, total pressure, and Br₂ pressure using a CO₂ TEA laser with an output less than 1 J pulse^–1 in order to optimize experimental conditions for¹³C separation. For example, we obtained CBr₂F₂ at a¹³C concentration of 55% in the irradiation of the mixture of 100-Torr CHClF₂ and 10-Torr Br₂ with the laser radiation at a wavenumber of 1045.02 cm^–1 and at a fluence of 3.4 J cm^–2. The mechanism for the IRMPD is discussed on the basis of observed results. Using 8-J pulses, we were able to obtain 1.9×10^–4 g of¹³C-enriched CBr₂F₂ (¹³C-atom fraction, 47%) per pulse under selected conditions. It is possible to produce 90% or higher¹³C by the second-stage IRMPD of the CBr₂F₂ in the presence of oxygen.