Potential of far-ultraviolet absorption spectroscopy as a highly sensitive quantitative and qualitative analysis method for aqueous solutions, part I: determination of hydrogen chloride in aqueous solutions

This paper reports the usefulness of far-ultraviolet (FUV) absorption spectroscopy in highly sensitive quantitative and qualitative analysis of aqueous solutions. We propose a totally new idea for the utilization of FUV spectroscopy in pure water and aqueous solution analyses. We use an absorption band near 170 nm due to an n --> sigma* transition of water. The intensity of the foot of this band, which can be observed in the 190-210 nm region by use of an ordinary ultraviolet-visible (UV-Vis) spectrometer, is very sensitive to changes in hydration and hydrogen bonds of water. To demonstrate the potential of FUV spectroscopy in analytical chemistry, we undertook three kinds of experiments. The first one is concerned with the discrimination of eight kinds of commercial natural mineral water. The eight kinds of mineral water can be discriminated straightforwardly from the spectral patterns in the 190-250 nm region without any spectral pretreatment or spectral analysis such as multivariate analysis. The second experiment is the determination of hydrogen chloride (HCl) in aqueous solutions. FUV spectra of aqueous solutions of HCl over a concentration of 0-20 ppm were measured. A calibration model for predicting the concentration of HCl in the aqueous solutions was developed based on the absorbance at 193 nm. This method does not require any spectral pretreatment or multivariate analysis. The correlation coefficient and standard error of prediction of the calibration model developed are 0.9987 and 0.18 ppm, respectively. The detection limit of the proposal method for the determination of HCl in aqueous solutions was estimated to be 0.5 ppm (13.7 microM). The determination of HCl was also tried for natural mineral water to which HCl solutions with the concentrations of 2, 4, 6, 8, 12, 16, and 20 ppm were artificially added. The third study was the determination of ammonia (NH3) and hydrogen peroxide (H2O2) in aqueous solutions containing both NH3 and H2O2. It has been found that the present method is also useful for the determination of the two-component system.     

Simultaneous electroanalysis of peroxyacetic acid and hydrogen peroxide

The electrochemical behavior of peroxyacetic acid (PAA) in the presence of hydrogen peroxide (H2O2) has been investigated using cyclic voltammetry and hydrodynamic techniques [rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry]. The results have been analyzed aiming at simultaneous electroanalysis of both species. Glassy carbon and gold electrodes were used for this investigation. It was found that the reduction of PAA, as well as H2O2, is highly sensitive to the electrode material; for example, at 100 mV s-1, the reduction peak potentials of PAA were 0.2 and -1.1 V at gold and glassy carbon electrodes, respectively. The well-separated steady-state limiting currents were obtained using a gold electrode for the reduction of both PAA and H2O2 and also a well-defined one for the oxidation of H2O2. On the basis of the RDE experiments, good calibration curves were obtained for both species over a wide range of their concentrations, for PAA and H2O2 in the range of 0.36 to 110 and 0.11 to 34 mM, respectively. The simultaneous and selective electroanalysis of PAA and H2O2 in their coexistence is demonstrated for the first time.     

Effect of poly(acrylic acid) on the preparation of thick silica films by electrophoretic sol–gel deposition of re-dispersed silica particles

Thick silica films were prepared by the electrophoretic sol–gel deposition technique in the presence of poly(acrylic acid) (PAA) using monodispersed silica particles; the particles were prepared by the sol–gel method, pre-heat treated and then re-dispersed in the mixture of H2O and ethanol. The weight of deposited silica films was maximized when 0.2 mass % of PAA against the whole amount of sol was added. The particles constructing the thick silica films were packed densely when the amount of added PAA was less than 0.2 mass%. The weight of the film increased with decrease in the content of H2O in the sol when a fixed amount of PAA was added. After the heat treatment of deposited films at 800 °C, crack-free silica films of about 30 m thickness were prepared. © 1998 Chapman & Hall     

Potential of far-ultraviolet absorption spectroscopy as a highly sensitive analysis method for aqueous solutions. Part II: monitoring the quality of semiconductor wafer cleaning solutions using attenuated total reflection

Far-ultraviolet (FUV) spectroscopy combined with attenuated total reflection (ATR) is employed for direct measurement of the concentrations of semiconductor wafer cleaning fluids such as SC-1 (aqueous solution of NH(3) and H(2)O(2)) and SC-2 (aqueous solution of HCl and H(2)O(2)). FUV spectra of these aqueous solutions in the 170-200 nm region are highly sensitive to changes in both hydrogen bonding and hydration. Although ATR measurement results in lower absorptivity compared to transmittance measurement, it is possible to increase absorption with greater evanescent wave penetration depth using a low refractive index internal reflection element (IRE). We adopt quartz as an IRE material. Since the refractive index of quartz becomes lower than that of water in the low energy side of an intense absorption band due to the n --> sigma* transition of water, the quartz IRE yields non-total reflection wavelength regions. However, near 175 nm the effective absorptivity of the tail of water's absorption band can be successfully enlarged, making the FUV-ATR technique suitable for measuring the concentrations of the components in the semiconductor wafer cleaning fluids. In the present study we prepared the same cleaning fluids as those used in actual semiconductor fabrication and measured their FUV-ATR spectra in the 150-300 nm wavelength range. It was found that even with the quartz IRE one can measure FUV-ATR spectra under total reflection conditions at 175 nm or above. We created calibration models for predicting both NH(3) and H(2)O(2) in the concentration ranges of 0-10% in SC-1 using multiple linear regression (MLR). The standard deviations of the models were 0.033% and 0.265% for NH(3) and H(2)O(2), respectively. The same procedure was repeated under the same conditions for HCl and H(2)O(2) in SC-2, yielding corresponding values of 0.018% for HCl and 0.178% for H(2)O(2).     

Simultaneous potentiometric determination of peracetic acid and hydrogen peroxide

A rapid and highly selective potentiometric method for the simultaneous analysis of peracetic acid (PAA) and hydrogen peroxide (H2O2) has been proposed, for the first time, using glassy carbon (GC) as an indicator electrode and I2/I- potential buffer. On the basis of the large difference in the reaction rates of PAA and H2O2 with I-, which was confirmed using stopped-flow spectrophotometry, a transient potential response corresponding to the reactions of the two species with I- was observed. The response times were typically a few seconds and several minutes for PAA and H2O2, respectively. The effects of the concentrations of molybdate catalyst, H+, I2, and I- in the potential buffer on the selectivity as well as the sensitivity were examined. The potential response obtained using the GC indicator electrode was found to be Nernstian over a wide range of their concentrations (typically from micromolar to millimolar) with slopes of 30.5 and 29.5 mV for PAA and H2O2, respectively (in close agreement with the theoretical value, that is, 29.6 mV). O2 was found to have no substantial effect on the potential change at the GC electrode in the present potential buffer.     

Nanoclays reinforced glass ionomer cements: dispersion and interaction of polymer grade (PG) montmorillonite with poly(acrylic acid)

Montmorillonite nanoclays (PGV and PGN) were dispersed in poly(acrylic acid) (PAA) for utilization as reinforcing filler in glass ionomer cements (GICs). Chemical and physical interaction of PAA and nanoclay (PGV and PGN) was studied. PAA–PGV and PAA–PGN solutions were prepared in different weight percent loadings of PGV and PGN nanoclay (0.5–8.0 wt%) via exfoliation-adsorption method. Characterization was carried out by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and fourier transform infrared (FTIR) spectroscopy. XRD results of PAA–PGN demonstrated that the interlayer space expanded from 12.83 to 16.03 Å indicating intercalation whereas the absence of the peak at d ₀₀₁ in PAA–PGV indicated exfoliation. XPS scans of PGV and PGN nanoclays depicted the main peak of O 1s photoelectron due to Si–O–M (M = Mg, Al, Fe) whereas, Si–O–Al linkages were identified by Si 2p or Si 2s and Al 2p or Al 2s peaks. The disappearance of the Na peak confirmed that PAA molecules exchanged sodium ions present on surface of silicate layers and significantly reduced the electrostatic van-der-Waals forces between silicate plates resulting in intercalation or exfoliation. FTIR spectra of PAA–nanoclay suspensions demonstrated the presence of a new peak at 1,019 cm^?1 associated with Si–O– stretching vibrations which increased with increasing nanoclays concentration. Information concerning the dispersion of nanoclay in PAA aqueous solutions, chemical reaction and increase interlayer space in montmorillonite nanoclay is particularly useful regarding dispersion and reinforcement of nanoclay in PAA.     

Ultraviolet-induced surface modification of polyurethane films in the presence of oxygen or acrylic acid vapours

An efficient surface functionalization of polyurethane (PU) films has been obtained by ultraviolet (UV)-assisted modification in the presence of oxygen or acrylic acid (AA) vapours. Film analyses were carried out by water contact angle measurements, X-ray photoelectron spectroscopy (XPS) and Near-edge X-ray absorption fine structure (NEXAFS). Film hydrophilicity increased with photolysis time in the presence of oxygen or AA vapours. Incorporation of COO and CO functional groups at the polymer surface after the UV-assisted treatments was observed. In addition, High resolution XPS and NEXAFS results showed that a thin film of poly (acrylic acid) (PAA) is formed over the PU films during the UV irradiation with AA vapours. The obtained results are compared with previous published oxygen and AA low-power plasma treatments. Similarity between both treatment methodologies is shown. UV surface functionalization and polymerization of PAA can be used instead of a traditional plasma treatment with the advantage of set-up simplicity and lower costs.     

Measurement of the Refractive Indices of H(2)SO(4)-HNO(3)-H(2)O Solutions to Stratospheric Temperatures

Refractive indices of various H(2)SO(4)-H(2)O, HNO(3)-H(2)O, and H(2)SO(4)-HNO(3)-H(2)O solutions were measured at four wavelengths in the visible (351.0, 533.5, 632.9, and 782.6 nm) over a temperature range from 30 to -60 degrees C. The temperature dependence has been determined for the first time to the authors' knowledge. This dependence is of importance for applications to atmospheric aerosols at low temperatures. In particular, it is shown that (1) the molar refractivity of the solutions is independent of temperature, whereas the temperature dependence of the refractive index arises solely through the temperature dependence of the solution's mass density, (2) the molar refractivities of H(2)SO(4) and HNO(3) in a ternary solution may be calculated as the weighted sum of the molar refractivities of two binary solutions evaluated at a concentration that corresponds to the total acid concentration, and (3) the H(2)O molar refractivity in the solutions may be taken equal to that of pure water. Although the data for the ternary system have been used for this model verification, data for binary H(2)SO(4)-H(2)O and HNO(3)-H(2)O solutions were used to improve the accuracy of the modeled refractive indices to better than 0.0017% or 0.15% for concentrations of 5-70 wt.% and wavelengths from the near ultraviolet to the near infrared (0.25-2 mum).     

Laser-induced breakdown spectroscopy of gas mixtures of air, CO2, N2, and C3H8 for simultaneous C, H, O, and N measurement

Laser-induced breakdown spectroscopy (LIBS) was applied for simultaneous measurement of the elements C, H, N, and O in CO2-air, C3H8-CO2, and C3H8-N2 gas mixtures at atmospheric pressure. A single 7-mm-diameter aperture at the sample chamber was used for 1064-nm Nd:YAG laser irradiation and plasma signal output to an echelle spectrometer. Double-pulse laser bursts of approximately 8-ns pulse width (FWHM) and 250-ns interpulse separation were applied to increase the plasma signal. Calibration curves of the LIBS signal versus the partial pressure or the atomic abundance ratios were taken by dilution series in intervals that are relevant in the combustion of heptane (C7H16) near an equivalence ratio of 1.     

Hydrothermal synthesis and photocatalytic activity of CdO2 nanocrystals

CdO(2) nanocrystals with different sizes were synthesized via the hydrothermal reaction of 3CdSO(4).8H(2)O and H(2)O(2) in 1.25-6.25 vol.% ammonia solutions at 100-140 degrees C for 12h. The resultant products were characterized by powder X-ray diffraction, transmission electron microscope, thermal gravimetric and differential scanning calorimetry, and UV-vis absorption spectra. It was concluded that the resultant products were pure cubic phase CdO(2) nanocrystals, and they would decompose at temperatures higher than 180 degrees C. In addition, degradation of methyl orange in aqueous solution (20.0mg/l) was carried out with the CdO(2) nanocrystals as photocatalyst under ultraviolet light irradiation. The experimental results showed that even a little amount (0.2g) of as-prepared CdO(2) nanocrystals could catalyze degradation of 500 ml methyl orange solution above 99% after 5h of illumination, and smaller size made for higher photocatalytic activity of CdO(2) nanocrystals.     

One-dimensional TiO2 nanomaterials: preparation and catalytic applications

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.     

Determination of selenium by inductively coupled plasma mass spectrometry utilizing a new hydride generation sample introduction system.

An inductively coupled plasma mass spectrometer with a newly designed continuous flow hydride generator was used for the determination of Se in biological materials. The design of the hydride generator was important in minimizing interference from HCl and in maximizing analytical sensitivity. Two sample preparation procedures incorporating either 3.8 or 7.2 M HCl in the final sample solutions were compared. Interference from Cu was eliminated by the addition of 0.2 M NaI to the sodium borohydride solution (3.8 M method) or by maintaining a high concentration of HCl in the sample solution (7.2 M method). The 3.8 M method had the advantage of minimizing exposure of expensive equipment to corrosive HCl fumes, whereas the 7.2 M method did not contaminate equipment with I and had no measurable sample-to-sample cross-contamination. In practice, cross-contamination from sample to sample in both methods was negligible during analysis. An important factor in minimizing cross-contamination from sample to sample was the elimination of the air bubble normally entrained between samples. Determination of isotopic tracer enrichment was linear from 0 to 320% enrichment, which provided a broad range for isotope dilution analysis. A detection limit of 6.4 pg of Se was observed under optimum conditions, whereas a detection limit of 1.3 ng of Se was found for routine analysis of 1-g samples of plant material. Selenium was accurately determined by isotope dilution analysis in a variety of biological reference materials.     

Transition frequencies and strengths of H217O and H218O: 6600 to 7640 cm(-1)

High-resolution spectra of O(17)- and O(18)-enriched water-vapor samples have been recorded with a Fourier transform spectrometer covering the region between 6600 and 7640 cmcm(-1). Experimental values of line positions and strengths of 1807 absorptions in the (120)-(000), (021)-(000), (200)-(000), (101)-(000), (002)-(000), bands of the two isotopic species were derived from the spectra. The analysis included the determination of accurate rotational levels belonging to the (120), (021), (200), (101), and (002) vibrational states of H(2)(17)O and H(2)(18)O.     

Chemical treatment of poly(lactic acid) fibers to enhance the rate of thermal depolymerization

When heated, poly(lactic acid) (PLA) fibers depolymerize in a controlled manner, making them potentially useful as sacrificial fibers for microchannel fabrication. Catalysts that increase PLA depolymerization rates are explored and methods to incorporate them into commercially available PLA fibers by a solvent mixture impregnating technique are tested. In the present study, the most active catalysts are identified that are capable of lowering the depolymerization temperature of modified PLA fibers by ca. 100 °C as compared to unmodified ones. Lower depolymerization temperatures allow PLA fibers to be removed from a fully cured epoxy thermoset resin without causing significant thermal damage to the epoxy. For 500 μm diameter PLA fibers, the optimized treatment involves soaking the fibers for 24 h in a solvent mixture containing 60% trifluoroethanol (TFE) and 40% H(2)O dispersed with 10 wt % tin(II) oxalate and subsequent air-drying of the fibers. PLA fibers treated with this procedure are completely removed when heated to 180 °C in vacuo for 20 h. The time evolution of catalytic depolymerization of PLA fiber is investigated by gel permeation chromatography (GPC). Channels fabricated by vaporization of sacrificial components (VaSC) are subsequently characterized by scanning electron microscopy (SEM) and X-ray microtomography (Micro CT) to show the presence of residual catalysts.     

PAMPS/PAA互穿双网络水凝胶的制备及强度研究

通过自由基溶液聚合法和互穿双网络技术(IPDN),合成包含第一网络PAMPS及第二网络PAA的高强度PAMPS/PAA互穿双网络水凝胶(IPDNH),探讨IPDNH的最佳制备条件、抗压缩性能影响因素。结果表明,PAMPS所占比例的提高及PAA交联剂用量的增大都使IPDNH的压缩强度呈现先增大后减小的趋势,而PAMPS交联剂用量的增大,则使压缩强度不断降低。当双网络的单体配比n(AMPS)/n(AA)=3.5/1,PAMPS交联剂用量为2%,引发剂用量为0.2%,PAA交联剂用量为0.5%,引发剂用量0.5%时,IPDNH的抗压缩强度可达58.3MPa,远大于普通水凝胶。     

Real-time analysis of methanol in air and water by membrane introduction mass spectrometry.

We present results for the near-real-time, on-line detection of methanol in both air and water using membrane introduction mass spectrometry (MIMS). In these experiments, we compare the sensitivity of a poly(dimethylsiloxane) (PDMS) membrane and an allyl alcohol (AA) membrane to the detection of methanol. In MIMS, the membrane serves as the interface between the sample and the vacuum of the mass spectrometer. Membrane-diffused water was used as the reagent ion (H3O+) for chemical ionization of methanol in an ion trap mass spectrometer. Linear calibration curves have been obtained for methanol using both PDMS and AA membranes. For PDMS, detection limits of methanol are 14 ppmv and 5 ppm in air and water, respectively. For AA, detection limits are 3.3 ppmv and 2 ppm in air and water, respectively. We demonstrate that the sensitivity of the analysis can be altered by the chemistry of the membrane. When the AA membrane is used, the sensitivity of MIMS is enhanced over that of PDMS by a factor of 8.5 for methanol in air and by a factor of 23.4 for methanol in water.     

Noble Metal-Free Reduced Graphene Oxide-Zn(x)Cd(1-x)S Nanocomposite with Enhanced Solar Photocatalytic H(2)-Production Performance

Design and preparation of efficient artificial photosynthetic systems for harvesting solar energy by production of hydrogen from water splitting is of great importance from both theoretical and practical viewpoints. ZnS-based solid solutions have been fully proved to be an efficient visible-light driven photocatalysts, however, the H(2)-production rate observed for these solid solutions is far from exciting and sometimes an expensive Pt cocatalyst is still needed in order to achieve higher quantum efficiency. Here, for the first time we report the high solar photocatalytic H(2)-production activity over the noble metal-free reduced graphene oxide (RGO)-Zn(x)Cd(1-x)S nanocomposite prepared by a facile coprecipitation-hydrothermal reduction strategy. The optimized RGO-Zn(0.8)Cd(0.2)S photocatalyst has a high H(2)-production rate of 1824 μmol h(-1) g(-1) at the RGO content of 0.25 wt % and the apparent quantum efficiency of 23.4% at 420 nm (the energy conversion efficiency is ca. 0.36% at simulated one-sun (AM 1.5G) illumination). The results exhibit significantly improved photocatalytic hydrogen production by 450% compared with that of the pristine Zn(0.8)Cd(0.2)S, and are better than that of the optimized Pt-Zn(0.8)Cd(0.2)S under the same reaction conditions, showing that the RGO-Zn(0.8)Cd(0.2)S nanocomposite represents one of the most highly active metal sulfide photocatalyts in the absence of noble metal cocatalysts. This work creates a green and simple way for using RGO as a support to enhance the photocatalytic H(2)-production activity of Zn(x)Cd(1-x)S, and also demonstrates that RGO is a promising substitute for noble metals in photocatalytic H(2)-production.     

Detection of trace water vapor in high-purity phosphine using cavity ring-down spectroscopy

The presence of trace water vapor in process gases such as phosphine, used for compound semiconductor epitaxial growth, can negatively affect the optical and electrical properties of the final device. Therefore, sensitive H2O measurement techniques are required to monitor precursor purity and detect unacceptable contamination levels. A commercial cavity ring-down spectrometer that monitors an H2O absorption line at a wavelength of 1392.53 nm was investigated for service in high purity PH3. Spectral parameters such as the line shape of water vapor in the presence of PH3 as well as background features due to PH3 were measured at different pressures and incorporated into the data analysis software for accurate moisture readings. Test concentrations generated with a diffusion vialbased H2O source and dilution manifold were used to verify instrument accuracy, sensitivity, linearity, and response time. H2O readings at 13.2 kPa corresponded well to added concentrations (slope=0.990+/-0.01) and were linear in the tested range (0-52.7 nmol mol-1). The analyzer was sensitive to changes in H2O concentration of 1.3 nmol mol-1 based on 3sigma of the calibration curve intercept for a weighted linear fit. Local PH3 absorption features that could not be distinguished from the H2O line were present in the purified PH3 spectra and resulted in an additional systematic uncertainty of 9.0 nmol mol-1. Equilibration to changing H2O levels at a flow rate of 80 std cm3 min-1 PH3 occurred in 10-30 minutes. The results indicate that cavity ring-down spectroscopy (CRDS) at 1392.53 nm may be useful for applications such as on-line monitoring (and dry-down) of phosphine gas delivery lines or the quality control of cylinder sources.     

Simultaneous determination of the (2)h/(1)h, (17)o/(16)o, and (18)o/(16)o isotope abundance ratios in water by means of laser spectrometry

We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative (2)H/(1)H, (17)O/(16)O, and (18)O/(16)O isotope abundance ratios in water. The method uses a narrow line width color center laser to record the direct absorption spectrum of low-pressure gas-phase water samples (presently 10 μL of liquid) in the 3-μm spectral region. It thus avoids the laborious chemical preparations of the sample that are required in the case of the conventional isotope ratio mass spectrometer measurement. The precision of the spectroscopic technique is shown to be 0.7‰ for δ(2)H and 0.5‰ for δ(17)O and δ(18)O (δ represents the relative deviation of a sample's isotope abundance ratio with respect to that of a calibration material), while the calibrated accuracy amounts to about 3 and 1‰, respectively, for water with an isotopic composition in the range of the Standard Light Antarctic Precipitation and Vienna Standard Mean Ocean Water international standards.     

Phase development and structural characterization of calcium phosphate ceramics-polyacrylic acid nanocomposites at room temperature in water-methanol mixtures

Calcium phosphate ceramics (CPCs) were prepared via an in-situ formation in the presence of polyacrylic acid (PAA) polymer under water-methanol (WM) mixture at room temperature. The PAA polymer was employed as both structure-directing agent and crystallization retardant to manipulate the development of resulting CPCs nano-crystallites which are observed to show a core-shell configuration with a thin layer of PAA molecules. A resulting phase evolution map with respect to the developing phases of calcium-deficient hydroxyapatite (CDHA), -tricalcium phosphate (-TCP), and an intermediate amorphous calcium phoshate (ACP) that were structurally and spectroscopically identified, was constructed in terms of fractions of water-to-methanol proportions and concentration of PAA. It is found that for the solutions in both water-rich and methanol-rich regions, pure CDHA and -TCP instead of intermediate ACP phase can be developed irrespective of the concentration of PAA, respectively. For conditions in between, i.e., with methanol fractions of 15%–90%, ACP appeared only when the PAA fell in a limited concentration range.