Flame‐retardancy of a Cellulosic Fabric by the Application of Synergistic Effect between Ammonium Bromide and Antimony(III) Oxide

The synergistic effect between ammonium bromide and antimony(III) oxide as a nondurable finish on the flammability of 100% woven plain cotton fabric (with a density of 144 g/m2, the number of yarns 21 per 10 mm), has been investigated in this study. The laundered totally-dried, weighed specimens were impregnated with suitable concentration individual aqueous ammonium bromide and/or antimony(III) oxide suspension solutions and some sets were impregnated with appropriate admixed solutions of the both chemicals. A vertical flame spread test was then carried-out to characterize the flammability of the samples. An acceptable synergistic effect was then experienced by using an admixed bath containing 0.1 molar ammonium bromide and 0.05 unit formal antimony trioxide solutions for impartation of flame-retardancy to a cotton fabric. The optimum mass of the mixture required to impart flame-retardancy was about 3.64 g of anhydrous additives per 100 g of fabric. The results obtained are in favor of Wall Effect Theory. Moreover synergistic effect indicating dehydration of the treated substrate by using this combination via thermogravimetry could be deduced.     

Combustion pathway of cotton fabrics treated by ammonium sulfate as a flame-retardant studied by TG

The effect of ammonium sulfate (NH₄)₂SO₄ on the flammability of 100% cotton woven fabric (plain 144 g m⁻², the number of yarns 21 per 10 mm) has been of interest in this study. The laundered bone-dried, massed fabrics were impregnated with suitable concentration of aqueous ammonium sulfate solutions by means of squeeze rolls, drying and conditioning. Afterwards the specimen’s resistance to burning has been determined. The optimum add-on value of ammonium sulfate to impart flame-retardancy to cotton fabric was in a range about 10.55–13.62 g anhydrous salt per 100 g fabric. Thermogravimetry (TG/DTG) of the pure cotton and the treated one with the above-mentioned sulfate as well as for pure salt were also accomplished and their TG curves were compared and commented to detect the combustion’s pathway of the supported substrate. TG data confirm major mass loss in treated cotton. It occurred well below at a punctual duration of the thermal degradation zone of the polymer. So fewer flammable volatiles and more char could be produced during combustion. The results obtained are in compliance with gas dilution theory and also chemical action theory.     

Dynamic and controlled rate thermal analysis of attapulgite

We have investigated the effect of magnesium chloride hexahydrate [MgCl₂·H₂O] as a nondurable finish on the flammability of 100% woven cotton fabric, (plain construction, with a density of 144 g m⁻², the number of yarns 21/10 mm). The laundered bone-dried, massed fabrics were impregnated with suitable concentrations of aqueous solution of the above-mentioned salt, by means of squeeze rolls. They were then dried horizontally in an oven at 110°C for 30 min. The optimum add-on value after the fulfillment of vertical flame spread test to donate flame-retardancy onto cotton fabric was obtained to be in the range of 6.73–8.30 g of the salt per 100 g fabric. Thermogravimetry (TG) of pure cotton, treated cotton and the salt was accomplished, and their TG curves were compared and commented. The results obtained are in favor of the ‘gas dilution theory’, chemical action theory and also in compliance with the ‘free radical theory’. The formation of sal ammoniac was proven by sprinkling concentrated ammonia upon the inflamed treated specimen.     

Ion-pair hollow-fiber liquid-phase microextraction of the quaternary ammonium surfactant dicocodimethylammonium chloride

A two-phase hollow-fiber (HF) liquid-phase microextraction (LPME) method was developed for determination of a quaternary ammonium compound surfactant, dicocodimethylammonium chloride, in aqueous samples. The porous HF was fixed on a metal rod support and was impregnated with approximately 6.6 μL of organic extractant, which was immobilized in the HF pores. Surfactant extraction was facilitated by addition of carboxylic acid to the sample forming neutral ion pairs with the quaternary ammonium compound. After extraction, the analyte was transferred from the organic extractant in the fiber pores by dissolving the 1-octanol into 100 μL methanol. The methanol extract was analyzed by liquid chromatography–mass spectrometry. The method was optimized (with optimized parameters in brackets) with regard to type of organic extractant (1-octanol), fiber length (2 cm), choice and concentration of anionic carrier (600 μg L⁻¹ octanoate), procedure of transfer to methanol (15-min sonication), sample volume (250 mL), extraction time (17 h), pH (10), and ionic strength (50 mM carbonate). Aspects influencing repeatability in LPME of (quaternary ammonium) surfactants are discussed. The enrichment factor achieved in 250-mL carbonate buffer was around 400. Due to matrix effects, the enrichment factors achieved when industrial process water was analyzed were 120 or about 30% of that in carbonate buffer. Detection limits of 0.3 μg L⁻¹ in carbonate buffer and 0.9 μg L⁻¹ in industrial process water were obtained. If the studied compound is seen as a model substance representing quaternary dialkylated dimethylated ammonium surfactants in general, the developed method may be applied to other quaternary ammonium surfactants.     

Imparting durable antimicrobial properties to cotton fabrics using quaternary ammonium salts through 4-aminobenzenesulfonic acid-chloro-triazine adduct

A 4-aminobenzenesulfonic acid-chloro-triazine adduct was successfully synthesized in a laboratory scale and treated with cotton fabrics in order to increase the anionic sites and thereby % exhaustion of cationic compounds. Two Quaternary Ammonium Salts (QAS) was investigated namely, Cetylpyridinum chloride (CPC) and Benzyldimethylhexadecyl ammonium chloride (BDHAC) which are widely accepted as strong antimicrobial agents. The reaction mechanism involved in the synthesis of the reactive adduct as well its application to cotton fabric were demonstrated in detail. The effects of application parameters, namely pH, temperature and liquor ratio were examined. The reaction efficiency was determined through monitored % exhaustion of the adduct by cotton fabric. Antimicrobial activity of the treated cotton sample was studied against Staphylococcus aureus according to AATCC test method 100-1999. Results obtained show that the treated fabric shows higher antimicrobial activity compared with the untreated fabric. The results depict also that % exhaustion decreases as the pH, temperature and liquor ratio increase. Moreover, the appropriate predictable empirical models were developed using Excel solver function incorporating interaction effects of all variables to predict the % exhaustion and the satisfactory results (R² > 0.98) were obtained.     

TG studies of synergism between red phosphorus (RP)–calcium chloride used in flame-retardancy for a cotton fabric favorable to green chemistry

The combined effect between calcium chloride and red phosphorus (RP) on the flame-retardancy of a cotton fabric (woven construction massing 152 g/m²) has been studied in this work. The laundered bone-dried massed samples were impregnated with suitable concentrations of individual aqueous red phosphorus suspensions and/or calcium chloride solutions and some bunches were impregnated with appropriate admixed solutions of the both chemicals. An acceptable synergistic effect was then experienced by using an admixed bath containing 0.20 F red phosphorus and 0.20 M calcium chloride for impartation of flame-retardancy to a cotton fabric. By using a vertical flame spread test the optimum mass of the mixture needed to donate flame-retardancy was obtained to be about 5.88 g anhydrous additives per 100 g dry fabric. Thermogravimetry (TG/DTG) results concerning untreated and treated cotton fabrics at the optimum addition were obtained and their curves were compared and commented, fortifying the flame spread tests outcomes. It can be deduced that the applied treatment functioned as a catalyst at the combustion’s temperature of the polymeric substrate and, thermosensibilized the combustion process. This synergism is in favor of green chemistry as well as the economical and industrial view points.     

Influence of ammonium chloride on growth and fatty acid production by spirulina platensis

Changes in growth and fatty acid content ofSpirulina platensis were examined after transferring cells into media containing various concentrations of ammonium chloride. Photosynthetic O₂ evolution rate decreased with increasing ammonium chloride concentration. Therefore, the algal growth was interrupted by ammonium chloride addition. On the other hand, total fatty acid content markedly increased after addition of ammonium chloride to a concentration of 15–50 mM and was maximized 40–48 h after addition of 25 mM ammonium chloride. The increases in palmitic and oleic acid content were especially remarkable. However, this began to decrease 48 h after the addition of 25 mM of ammonium chloride. Also, γ-linolenic acid content increased continuously during a 72-h incubation. As a result,Spirulina platensis cells containing about 2% γ-linolenic acid were obtained by ammonium chloride treatment, representing an increase of 1.5–2-fold compared to untreated cells.     

XRD characterization of the ashes from a burned cellulosic fabric impregnated with magnesium bromide hexahydrate as flame-retardant

The effect of magnesium bromide hexahydrate [MgBr₂·6H₂O] as a nondurable finish on the flammability of 100% cotton fabric, (woven construction, massing 150 g m⁻²) has been investigated. The laundered bone-dried, massed fabrics were impregnated with various concentrations of the aqueous above-mentioned salt solutions by means of squeeze rolls and drying in an oven at 110°C for 30 min. The specimens were then cooled in a desiccator, re-massed with an analytical balance and kept under standard conditions before the fulfillment of the vertical flame spread test. After several experiments the optimum add-on values to impart flame-retardancy expressed in g anhydrous magnesium bromide hexahydrate per 100 g fabric were determined to be about 5.6%. The ashes of the treated specimens were subjected to X-ray diffraction analysis (XRD), and the result was compared with data for pure MgO powder and/or MgBr₂ specimens. Consequently the existence of MgO was detected in the ashes.     

TG of a cotton fabric impregnated by sodium borate decahydrate (Na2B4O7·10H2O) as a flame-retardant

The effect of sodium borate decahydrate as a nondurable treatment on the flammability of 100% cotton fabric (woven plain 150 g m⁻²) has been investigated in this paper. The laundered bone-dried massed samples were impregnated with suitable concentrations of sodium borate decahydrate. Each bunches of fabrics were dipped into individual aqueous solutions of the salt, followed by means of squeeze rolls and drying at 110°C. By using a ‘vertical flame spread test’ the optimum add-on values to impart flame-retardancy onto cotton fabric was determined to be as 4.24 g salt per 100 g fabric. The objective of this study is thermogravimetry (TG) investigation of pure cotton, treated one with the salt at its optimum efficiency. So that outcomes could be compared and commented, finally the results obtained are in favor of ‘Chemical action theory’, ‘Condensed phase retardation’, ‘Dust or wall effect theory’ and also ‘Gas dilution theory’.     

Synthesis and Evaluation of Technical Properties of Novel Cationic Mono‐s‐chloro Triazinyl (MCT) Reactive Dyes on Cotton

Two novel cationic mono‐s‐chloro triazinyl (MCT) reactive dyes together with their analogues were synthesized via reacting an N,N‐dimethyl dodecylamine with p‐nitrobenzyl bromide. The resultant was reduced using stannous chloride and hydrochloric acid to produce the primary amine. The quaternary ammonium salt containing primary amine was then diazotized and coupled to H‐acid/J‐acid reacted with cyanuric chloride and sulfanilic acid. The analogue dyes were prepared via the same route without quaternary ammonium salt making stage. The dyes were characterized using FTIR, ¹H NMR, UV‐Vis spectroscopy and elemental analysis. The substantivity, exhaustion and fixation of the dyes were investigated on cotton fabric. It was found that these functional dyes could be effectively introduced to cotton for achieving simultaneous coloration and functional finishing effects. All the dyed fabrics exhibited softening efficacy. The washing and light fastness of the dyed samples were further studied.     

The antibacterial finish of cotton via sols containing quaternary ammonium salts

The sols containing quaternary ammonium salts were prepared via sol-gel process. The effects of the molar rate of HCl, H₂O and EtOH to TEOS on the sol viscosity were investigated in detail. Cetyltrimethylammonium bromide (CTAB), Octadecyl dimethyl benzyl ammonium chloride (DC) and Ethylene-Bis (Octadecyl trimethyl ammonium chloride) [E-Bis(OTAC)]were added in the sols and applied to cotton samples by treated. The antibacterial activities of the samples were assessed against both Escherichia coli and Staphylococcus aureus bacteria. The samples treated by E-Bis(OTAC) sol exhibited the satisfactory antibacterial activity that resulted from the more microorganism adsorption and hydrophobicity. The antibacterial activities were still excellent after 10 times washings comparison with the control samples.     

Thermogravimetric Studies of Deposited Potash Impregnated for Flame-Retardancy into a Cotton Fabric

The effect of potash as a nondurable finish on the flammability of 100% cotton fabric （plain 180 g/m^2） was investigated. The bone-drled weighed fabrics were dipped into suitable concentrations of potash, with a volume of 100 mL at 20-2℃. The impregnation was followed by means of squeeze rolls and drying at 110 ℃. The samples were then reweighed with analytical precision. After conditioning overnight by using our ＂vertical flame tester＂ the optimum add-on values to impart flame-retardancy to cotton fabric was determined and expressed by 0.80 g of potash per 100 g fabric to be an efficient addition. Thermogravimetric analysis of pure cotton, treated cotton with potash at its optimum efficiency for donation of flame-retardancy into cotton fabric was fulfilled and the thermograms were compared and commented. The effectiveness of this hydroxide was attributed to the heat dissipation by the remaining consumed material during the combustion. The results obtained are in favor of ＂Dust or Wall Effect Theory＂.     

Modified bentonite by polyhedral oligomeric silsesquioxane and quaternary ammonium salt and adsorption characteristics for dye

To remove methylene blue dye from water by adsorption, bentonites were modified by polyhedral oligomeric silsesquioxane (POSS) and three kind of quaternary ammonium surfactants (dodecyl trimethyl ammonium bromide, tetrabutyl ammonium bromide, cetyl trimethylammonium bromide) in aqueous solution. Systematic adsorption experiments were carried out, the adsorption mechanism was studied, and the factors governing the adsorption of methylene blue on modified bentonite were discussed. The adsorption capacity of methylene blue on all three modified bentonites in 1000 mg·L⁻¹ solutions quickly reached equilibrium within 2000 s, and the removal rate was basically 100%; however, the removal rate in raw bentonite samples was only 60%. The pseudo second-order kinetic model can provide satisfactory kinetic data fitting. The obtained adsorption isotherms fit well with the Dubinin-Radushkevich isotherm model. The thermodynamic results showed that the adsorption process was a spontaneous endothermic physical adsorption process. With increasing pH and KCl concentration, the removal of methylene blue increased significantly. The results of this study confirmed that the modified bentonite is a candidate material as a cationic dye adsorbent.     

Cyclocopolymerization of allyl‐acrylate quaternary ammonium salts with diallyldimethylammonium chloride

A series of copolymers of N,N‐dialkyl‐N‐2‐(methoxycarbonyl)allyl allyl ammonium chloride, N,N‐dialkyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride, and N,N‐dialkyl‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide with diallyldimethylammonium chloride (DADMAC) were prepared in water at 60 °C with 2,2′‐azo‐bis(2‐amidinopropane)dihydrochloride. A strong effect of ester substituents on cyclopolymerization was observed. The methyl and ethyl ester monomers showed high cyclization efficiencies during homopolymerizations and copolymerizations. Unexpectedly, the t‐butyl ester derivatives showed high crosslinking tendencies. Water‐soluble copolymers were obtained only with a decrease in the molar fraction of t‐butyl ester monomer below 30%. Relative reactivities of the allyl‐acrylate monomers in photopolymerizations were compared with the relative reactivity of DADMAC. Allyl‐acrylate monomers were much more reactive than DADMAC; the photopolymerization rate decreased in the following order: N,N‐morpholine‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide > N,N‐piperidyl‐N‐2‐(t‐butoxycarbonyl)allyl allyl ammonium bromide > N,N‐dibutyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride > N,N‐piperidyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride ∼ N,N‐morpholine‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride ∼ N,N‐piperidyl‐N‐2‐(methoxycarbonyl)allyl allyl ammonium chloride > N‐methyl‐N‐butyl‐N‐2‐(ethoxycarbonyl)allyl allyl ammonium chloride. Intrinsic viscosities of the polymers measured in 0.09 M NaCl ranged from 1.06 to 3.20 dL/g. The highest viscosities were obtained for copolymers of the t‐butyl ester monomers with piperidine and morpholine substituents. The copolymer of the t‐butyl ester with piperidine substituent and DADMAC was hydrolyzed in acid to give a polymer with zwitterionic character. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 640–649, 2001     

Synthesis and cyclopolymerization of novel allyl‐acrylate quaternary ammonium salts

Novel allyl‐acrylate quaternary ammonium salts were synthesized using two different methods. In the first (method 1), N,N‐dimethyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium bromide and N,N‐dimethyl‐N‐2‐(tert‐butoxycarbonyl)allyl allylammonium bromide were formed by reacting tertiary amines with allyl bromide. The second (method 2) involved reacting N,N‐dialkyl‐N‐allylamine with either ethyl α‐chloromethyl acrylate (ECMA) or tert‐butyl α‐bromomethyl acrylate (TBBMA). The monomers obtained with the method 2 were N,N‐diethyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium chloride, N,N‐diethyl‐N‐2‐(tert‐butoxycarbonyl)allyl allylammonium bromide, and N,N‐piperidyl‐N‐2‐(ethoxycarbonyl)allyl allylammonium chloride. Higher purity monomers were obtained with the method 2. Solution polymerizations with 2,2′‐azobis(2‐amidinopropane) dihydrochloride (V‐50) in water at 60–70°C gave soluble cyclopolymers which showed polyelectrolyte behavior in pure water. Intrinsic viscosities measured in 0.09M NaCl ranged from 0.45 to 2.45 dL/g. ¹H‐ and ¹³C‐NMR spectra indicated high cyclization efficiencies. The ester groups of the tert‐butyl polymer were hydrolyzed completely in acid to give a polymer with zwitterionic character. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 901–907, 1999     

Ion-trap versus quadrupole for analysis of quaternary ammonium herbicides by LC-MS

Summary An ion-trap mass spectrometer for determination of quaternary ammonium herbicides in water samples is evaluated. Implementation of the method previously optimized in a quadrupole mass spectrometer (VG Platform II) in an ion-trap (LCQ) required modifications to the sample inlet of the electrospray source. Quality parameters were established and detection limits, after trace enrichment, range 5–50 ng L⁻¹. Good reproducibilities (day-to-day and run-to-run) <12% were obtained. The method was applied to analysis of spiked samples and the results were comparable with those determined using a quadrupole mass spectrometer.     

Detection of copper(II) sulfate’s uniformity and its thermal behavior in flammability of cotton fabric

Blue vitriol (copper(II) sulfate pentahydrate), CuSO₄·5H₂O has been chosen and investigated for its effectiveness as a flame-retardant, when impregnated into cotton fabric (cotton with a plain structure; woven 180 g m⁻², with 22 numbers of yarns per 10 mm). Using the vertical flame test, the extent of resistance to burning of the specimens has been determined. The impregnation was accomplished via dipping and stirring of bone-dried, weighed fabrics into the individual and suitable concentrations of the salt at room temperature. Afterwards the samples were squeeze rolled and dried horizontally at 110°C for 30 min in an oven and cooled in a desiccator and reweighed with an analytical precision. They were then kept under ordinary conditions overnight prior the fulfillment of the vertical flame test. The efficient quantities of the aforesaid salt expressed in g per 100 g dry fabric have been determined in an average figure of 12.75%. Estimation of uniformity in a selected sample was carried out via a spectrophotometer and results are in favor of the heterogeneous distribution of the salt in the fabric’s middle sectors. However initial and final parts of specimen showed to be rather uniformed. Thermogravimetric analysis of the pure cotton and the treated ones with insufficient and effective amounts of the salt were fulfilled and their thermograms were compared and commented. The results obtained for the effect of copper(II) sulfate comply with ‘The Dust or Wall Effect Theory’. This action is also assigned to the condensed phase retardation.     

Optimization of ammonium nitrate concentration in single-stage continuous cultures of Aspergillus niger with biomass retention

The effect of ammonium nitrate concentration in the citric acid biosynthesis by Aspergillus niger NC-12 in single-stage continuous cultures with biomass retention was investigated. Experiments were carried out in a BIOMER laboratory fermenter with 5 dm³ working volume. At the initial stage of each cultivation, the substrate in the bioreactor contained 1.5 g NH₄NO₃ dm⁻³. After 120 h onwards, the bioreactor was fed continuously at a constant dilution rate of 0.009 h⁻¹. NH₄NO₃ concentration in the feed was varied from one culture to another, ranging between 0.5 g dm⁻³ and 2.5 g dm⁻³. Promising results were obtained when NH₄NO₃ concentration of 1.5 g dm⁻³ was used. The observed concentration of citric acid (c _P) and yield of citric acid with respect to the introduced sucrose (Y _P/S) were 117.88 g dm⁻³ and 78.59 %, respectively. The efficiency coefficient of citric acid biosynthesis (K _ef) was very high, amounting to 83.38. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

The use of Chromazurol S in the presence of a mixture of cationic and non-ionic surfactants for the spectrophotometric determination of iron in cereals

Simple and sensitive methods for the spectrophotometric determination of iron(III) in food, based on the formation of coloured complexes of Fe(III) with Chromazurol S (CAS) in the presence of tetradecyltrimethylammonium bromide (TTA) or octadecyltrimethylammonium chloride (ODTA) and Triton X-100 (TX100), have been developed. Optimum pH and the concentrations of CAS, TTA, ODTA, and TX100 ensuring maximum absorbance have been determined. For the Fe-CAS-TTA-TX100 system the molar absorptivity is 1.12 × 10⁵ L/(mol cm) at 650 nm; for Fe-CAS-ODTA-TX100 it is 1.35 × 10⁵ L/(mol cm) at 659.5 nm. Beer’s law was obeyed for iron concentration in the range 0.08–0.56 μg/mL for the complex Fe-CAS-TTA-TX100 and 0.08–0.64 μg/mL for Fe-CAS-ODTA-TX100. The influence of several interfering ions has been discussed. The stoichiometry of the complexes was established by applying Job’s method. The more sensitive method, based on the Fe-CAS-ODTA-TX100 system, has been applied to the determination of iron in cereals. To evaluate the accuracy of the elaborated method, the determined content of Fe was compared to the declared value as well as to the result obtained by the reference ICP-OES method.     

Cotton fabrics treated with hybrid organic–inorganic coatings obtained through dual-cure processes

Cotton fabrics were treated with a hybrid organic–inorganic coating obtained through a dual-cure process, i.e. a photopolymerization reaction followed by a thermal treatment for promoting the formation of silica phases through a sol–gel process. To this aim, different amounts of a silica precursor were added to an acrylic UV-curable formulation in the presence of a suitable coupling agent. The thermo-mechanical properties of the treated fabrics were investigated and correlated to the composition and morphology of the hybrid organic–inorganic system. Furthermore, their flame retardancy and combustion behavior were evaluated by flammability tests and cone calorimetry and compared with the performances of pure cotton.