Experimental investigation on the spread of aqueous foam over ethanol surface

The presence of ethanol has an adverse effect on foam spreading, and ethanol fire is difficult to extinguish with aqueous fire-fighting foams. Thus, it is necessary to explore the foam formulation suitable for ethanol fuels and study the spreading behavior of foam over ethanol surface. In the current work, stable foams based on hydrocarbon surfactant (SDS), fluorocarbon surfactant (FC1157), and polymers (XG) were prepared by using the compressed-air foam system. The spreading behaviors of foam on polar ethanol and non-polar heptane surface were observed and compared. Furthermore, the effects of stabilizer concentrations, foam flow rates and expansion ratios on foam spreading performance were investigated, respectively. The results indicate that aqueous SDS foam can spread on the heptane layer continuously, but it is difficult to cover the ethanol surface. The addition of XG and FC1157 can synergistically improve the spreading performance of aqueous foam over ethanol. Depending on stabilizer concentrations, there are remarkable differences in foam spreading behaviors. Besides, different foam application parameters including expansion ratios and foam flow rates significantly affect the foam spreading rate, despite the same foam formulation. The research methods and results guide the optimal design of foam formulations as well as the practical application of aqueous foam for ethanol fire extinguishment.     

The physicochemical and fire extinguishing performance of aqueous film-forming foams based on a class of short-chain fluorinated surfactants

Aqueous film-forming foams (AFFFs) are an important for fire extinguishing, and their key ingredient is fluorinated surfactant. In recent years, traditional long-chain fluorinated surfactants have been banned by most countries because of their persistence, bio-accumulation and toxicity. Therefore, increased attention has been paid to the research and development of short-chain fluorinated surfactants. As is well known, the introduction of hydrophilic or hydrophobic groups in a surfactant affects its surface activity, and therefore, the fire extinguishing performance of AFFFs. In this work, a series of short-chain fluorosurfactant-based AFFFs with different hydrophobic chain lengths were prepared. The physicochemical performance of mixed systems (fluorinated surfactant plus sodium hexanesulfonate), including surface activity, spreading ability, foam expansion, drainage time, and the fire extinguishing and burn-back performance of AFFFs were studied. The results show that the critical micelle concentration (CMC) and the surface tension (γ_CMC) at the CMC of mixed systems at 25°C are lower than 7.68 mmol/L and 16.51 mN/m, respectively. For mixed systems, the average spreading rate is more than 1.09 cm/s, the foam expansion is over 7.1, and the drainage time is greater than 3.28 min. The fire extinguishing time of AFFFs on fuels is less than 51 s while the burn-back time is more than 15.18 min. The results imply a potential application prospect of the short-chain fluorinated surfactants in AFFFs.     

Synergistic Effects between Anionic and Sulfobetaine Surfactants for Stabilization of Foams Tolerant to Crude Oil in Foam Flooding

In foam flooding, foams stabilized by conventional surfactants are usually unstable in contacting with crude oil, which behaves as a strong defoaming agent. In this article, synergistic effects between different surfactants were utilized to improve foam stability against crude oil. Targeted to reservoir conditions of Daqing crude oil field, China (45 °C, salinity of 6778 mg L⁻¹, pH = 8–9), foams stabilized by typical anionic surfactants fatty alcohol polyoxyethylene ether sulfate (AES) and sodium dodecyl sulfate (SDS) show low composite foam index (200–500 L s) and low oil tolerance index (0.1–0.2). However, the foam stability can be significantly improved by mixing the anionic surfactant with a sulfobetaine surfactant, which behaves as a foam stabilizer increasing the half-life of foams, and those with longer alkyl chain behave better. As an example, by mixing AES and SDS with hexadecyl dimethyl hydroxypropyl sulfobetaine (C₁₆HSB) at a molar fraction of 0.2 (referring to total surfactant, not including water), the maximum composite foaming index and oil tolerance index can be increased to 3000/5000 L s and 1.0/4.0, respectively, at a total concentration between 3 and 5 mM. The attractive interaction between the different surfactants in a mixed monolayer as reflected by the negative β^s parameter is responsible for the enhancement of the foam stabilization, which resulted in lower interfacial tensions and therefore negative enter (E), spreading (S), and bridging (B) coefficients of the oil. The oil is then emulsified as tiny droplets dispersed in lamellae, giving very stable pseudoemulsion films inhibiting rupture of the bubble films. This made it possible to utilize typical conventional anionic surfactants as foaming agents in foam flooding.     

An Analytically Defined Fire‐Suppressing Foam Formulation for Evaluation of Fluorosurfactant Replacement

A 4‐component, analytically defined, reference fluorosurfactant formulation (Ref‐aqueous film forming foam [AFFF]) composed of 0.3% fluorocarbon‐surfactant concentrate (Capstone 1157), 0.2% hydrocarbon‐surfactant concentrate (Glucopon 215 UP), and 0.5% diethylene glycol mono butyl ether by volume in distilled water was found to have rapid fire extinction comparable to a commercial AFFF in tests conducted on a bench scale and a large scale (28 ft², part of US Military Specification, MIL‐F‐24385F). The Ref‐AFFF was analytically characterized to provide the identity and quantity of the chemical structures of the surfactant molecules that were lacking for commercial AFFF formulations. To arrive at an acceptable Ref‐AFFF formulation, 3 candidate formulations containing different hydrocarbon surfactants in varying amounts were evaluated and ranked relative to a commercial AFFF using a bench‐scale fire‐extinction apparatus; varying the hydrocarbon surfactant was found to affect the fire‐extinction time. The ranking was confirmed by the large‐scale tests suggesting that the bench‐scale apparatus is a reasonable research tool for identifying surfactants likely to succeed in the large‐scale test. In the future, replacing the fluorocarbon surfactant with an alternative surfactant in the Ref‐AFFF enables a direct comparison of fire extinction and environmental impact to identify an acceptable fluorine‐free formulation.     

碳氢/有机硅/低碳醇三元系泡沫及抑制煤自燃的效果分析

泡沫灭火剂是常用的火灾扑救方法之一,但常规泡沫灭火剂存在半衰期短,析液、聚并迅速而影响灭火效能的问题,基于火灾化学和活性剂技术,提出碳氢表面活性剂SDS、有机硅表面活性剂LS-99和低碳醇的三元系泡沫体系,并系统探究碳氢/有机硅/低碳醇的复配配比。通过表面张力、发泡高度、稳泡系数的大量测试,发现LS-99的临界胶束浓度为0.0083%。LS-99和SDS二元系在降低表面张力、提升发泡高度和稳泡系数方面具有良好的协同增效作用。在此基础上引入适量浓度的能够延缓泡沫析液、聚并的异丁醇,设计出了性能优良的碳氢/有机硅/低碳醇泡沫灭火剂。LS-99、SDS和异丁醇的质量分数为0.1%时,测试结果表明SDS/LS-99/醇三元系泡沫的发泡倍数可达52.5倍,25%析液时间可达210 s,300 s时的稳泡系数高达0.958,半衰期远超常规泡沫。煤自燃的灭火抑制实验表明,SDS/LS-99/醇三元系泡沫作用下,煤自燃各反应阶段的活化能相较于空气氛围均增大,反应难度增强;最大失重速率下降,反应剧烈程度减弱。初期吸热阶段的吸热量为78.3 J/g,大于空气氛围下煤氧复合的吸热量,吸热增幅高达2.16倍。放热阶段的放热量为1765.4 J/g,相较于空气氛围放热降幅达到15.15%,表明SDS/LS-99/醇三元系泡沫对煤自燃具有良好的灭火效果。     

Stabilization of natural gas foams using different surfactants at high pressure and high temperature conditions

Natural gas foam can be used for mobility control and channel blocking during natural gas injection for enhanced oil recovery, in which stable foams need to be used at high reservoir temperature, high pressure and high water salinity conditions in field applications. In this study, the performance of methane (CH₄) foams stabilized by different types of surfactants was tested using a high pressure and high temperature foam meter for surfactant screening and selection, including anionic surfactant (sodium dodecyl sulfate), non-anionic surfactant (alkyl polyglycoside), zwitterionic surfactant (dodecyl dimethyl betaine) and cationic surfactant (dodecyl trimethyl ammonium chloride), and the results show that CH₄-SDS foam has much better performance than that of the other three surfactants. The influences of gas types (CH₄, N₂, and CO₂), surfactant concentration, temperature (up to 110°C), pressure (up to 12.0 MPa), and the presence of polymers as foam stabilizer on foam performance was also evaluated using SDS surfactant. The experimental results show that the stability of CH₄ foam is better than that of CO₂ foam, while N₂ foam is the most stable, and CO₂ foam has the largest foam volume, which can be attributed to the strong interactions between CO₂ molecules with H₂O. The foaming ability and foam stability increase with the increase of the SDS concentration up to 1.0 wt% (0.035 mol/L), but a further increase of the surfactant concentration has a negative effect. The high temperature can greatly reduce the stability of CH₄-SDS foam, while the foaming ability and foam stability can be significantly enhanced at high pressure. The addition of a small amount of polyacrylamide as a foam stabilizer can significantly increase the viscosity of the bulk solution and improve the foam stability, and the higher the molecular weight of the polymer, the higher viscosity of the foam liquid film, the better foam performance.     

泡沫灭火剂中全氟辛烷磺酸类物质的管控行为及替代物研究进展

全氟辛烷磺酸（perfluorooctane sulfonic acid, PFOS）使水成膜泡沫灭火剂（aqueous film forming foam,AFFF）具有较好的耐高温和抗烧能力,但由于PFOS的难降解性、生物富集性及毒性,国内外相继对PFOS类物质进行了管控。本文简述和分析了泡沫灭火剂中PFOS类物质的管控行为及替代物研究,分析表明管控行动逐步从限制走向淘汰,研究泡沫灭火剂中PFOS类物质的替代物极为迫切;替代物的研究方向主要有两个,一个是泡沫灭火剂中短氟碳链类表面活性剂研究及短氟碳链泡沫灭火剂的灭火效果验证,但短氟碳链类表面活性剂可能存在长期环境持久性的问题;另一个是泡沫灭火剂中无氟类表面活性剂的研究,如有机硅表面活性剂、甜菜碱型表面活性剂、纯化皂苷表面活性剂,但无氟类表面活性剂可能会影响无氟泡沫灭火剂的表面活性、灭火能力、灭火效果等。泡沫灭火剂中PFOS类物质的替代物研发尚任重而道远。     

Synthesis and Application of Perfluoroalkyl Quaternary Ammonium Salts in Protein-Based Fire-Fighting Foam Concentrates

Nine perfluoroalkyl quaternary ammonium salts containing a perfluorinated tail were synthesized in order to evaluate their properties as additives in protein-based fire-fighting foam concentrates. They were obtained in high yield starting from (perfluoro-n-octyl)methyl oxirane via a two-step reaction scheme. Their structures were identified by Fourier-transform infrared spectroscopy and elemental analysis. Surface tension, interfacial tension, critical micellar concentration, and spreading coefficient of aqueous solutions of the synthesized compounds were first determined. Synthetic perfluoroalkyl quaternary ammonium salts were then added at reduced concentration (0.5 wt.%) to a commercial protein-based fire-fighting foam concentrate and their effects on foam spreading properties were further investigated via five specific laboratory tests: sealing time test, burn back time test, foam expansion test, drain time test, and foam flowing test. Results showed that the perfluoroalkyl quaternary ammonium salts strongly influence surface and extinguishing properties of protein-based fire-fighting foam concentrates, producing stable foams able to spread spontaneously over hydrocarbons and forming aqueous films with enhanced organic-vapor sealing properties.     

Bulk and bubble-scale experimental studies of influence of nanoparticles on foam stability

Influence of silicon oxide(SiO_2) and aluminum oxide(Al_2O_3) nanoparticles on the stability of nanoparticles and sodium dodecyl sulfate(SDS) mixed solution foams was studied at bulk and bubble-scale. Foam apparent viscosity was also determined in Hele-Shaw cell In order to investigate the foam performance at static and dynamic conditions. Results show that the maximum adsorption of surfactant on the nanoparticles occurs at 3 wt% surfactant concentration. Foam stability increases while the foamability decreases with the increasing nanoparticle concentration. However, optimum nanoparticle concentration corresponding to maximum foam stability was obtained at 1.0 wt% nanoparticle concentration for the hydrophilic SiO_2/SDS and Al_2O_3/SDS foams. Foam performance was enhanced with increasing nanoparticles hydrophobicity. Air-foams were generally more stable than CO_2 foams.Foam apparent viscosity increased in the presence of nanoparticles from 20.34 mPa·s to 84.84 mPa·s while the film thickness increased from 27.5 μm to 136 μm. This study suggests that the static and dynamic stability of conventional foams could be improved with addition of appropriate concentration of nanoparticles into the surfactant solution. The nanoparticles improve foam stability by their adsorption and aggregation at the foam lamellae to increase film thickness and dilational viscoelasticity. This prevents liquid drainage and film thinning and improves foam stability both at the bulk and bubble scale.     

温度对高浓度SDS水溶液泡沫稳定性及分离的影响

高浓度表面活性物质的分离是泡沫分离过程的难题,也是制约泡沫分离技术应用于工业化生产的瓶颈.为了解决高浓度表面活性物质泡沫分离的难题,以阴离子表面活性剂十二烷基硫酸钠(SDS)水溶液为体系,研究了在其临界胶束浓度(CMC)附近时,温度对SDS水溶液气泡直径、泡沫稳定性、富集比及回收率的影响.结果表明:温度对高浓度表面活性物质的泡沫分离有显著影响.当SDS水溶液浓度分别为1.2、2.3、3.5g·L-1,温度从30℃升高到70℃时,泡沫稳定性先增大后减小,在pH 6.9、表观气速2.4×10-3 m·s-1、装液量200 mL的操作条件下,气泡直径先减小后增大,富集比提高了3～5倍,回收率降低了34％～65％.     

泡沫分离法提取乙醇水体系中甲基橙

采用泡沫分离法对含甲基橙的乙醇水溶液进行了提取研究. 考察了乙醇体积分数、气体流量、pH、甲基橙浓度和表面活性剂浓度对提取效果的影响,并对泡沫分离乙醇-水体系中提取中药有效成分的可行性进行了探讨. 结果表明,以十六烷基三甲基溴化铵(CTAB)为表面活性剂,在乙醇体积分数25%的乙醇-水体系中,在pH 6.0、气速80 mL/min、甲基橙浓度35 mg/L及CTAB浓度80 mg/L的操作条件下,甲基橙的富集比为14.38,回收率在98.5%以上. 在一定范围内提高表面活性剂浓度或加入稳泡剂以削弱乙醇的消泡作用,从而将泡沫分离技术应用于乙醇-水体系中中药有效成分的提取是可能的.     

Rigid polyurethane foams based on soybean oil

Both HCFC‐ and pentane‐blown rigid polyurethane foams have been prepared from polyols derived from soybean oil. The effect of formulation variables on foam properties was studied by altering the types and amounts of catalyst, surfactant, water, crosslinker, blowing agent, and isocyanate, respectively. While compressive strength of the soy foams is optimal at 2 pph of surfactant B‐8404, it increases with increasing the amount of water, glycerin, and isocyanate. It also increases linearly with foam density. These foams were found to have comparable mechanical and thermoinsulating properties to foams of petrochemical origin. A comparison in the thermal and thermo‐oxidative behaviors of soy‐ and PPO‐based foams revealed that the former is more stable toward both thermal degradation and thermal oxidation. The lack of ether linkages in the soy‐based rather than in PPO‐based polyols is thought to be the origin of improved thermal and thermo‐oxidative stabilities of soy‐based foams. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 467–473, 2000     

Effect of Aqueous Film‐Forming Foams on the Evaporation Rate of Hydrocarbon Fuels

A class of firefighting foams, known as aqueous film‐forming foam (AFFF), has the ability to form a film by spreading on the free surface of some hydrocarbon fuels. To find out whether this film could reduce the evaporation losses of volatile hydrocarbons, the evaporation rates of fuels covered with a film of AFFF were measured by weighing the fuel at different time intervals. The results proved that the addition of aqueous surfactant solutions on the fuels is not always synonymous to the reduction of evaporation rates, but sometimes it might also cause an increase. However, it was found that polyethylene glycol could modify AFFF in a way that it can form a protective permanent film on the surface of a fuel such as kerosene, thereby leading to a reduction of evaporation losses.     

低碳醇改性无氟泡沫的性能分析与扑灭油池火的实验研究

针对现有氟碳类泡沫灭火剂关键组分PFOS因国际环境公约出于环保和健康而限用,以及现有泡沫灭火剂还存在析液速度快而影响灭火能效等问题,在前人及团队探究无氟泡沫复配方案基础上,基于火灾化学理论与表面活性剂技术,遴选碳氢/有机硅表面活性剂(LS-99/SDS)为基剂,通过引入可改善气泡聚并的低碳醇(乙醇、正丙醇和异丁醇)调控泡沫的发泡倍数和25%析液时间等性能,开展含醇泡沫和无醇泡沫的灭火对比实验,考察低碳醇引入后的泡沫灭火能效。结果表明,引入适量浓度低碳醇可显著影响LS-99/SDS复配体系的发泡倍数和25%析液时间。相比乙醇和正丙醇,当异丁醇质量分数为0.1%时,可有效延缓含醇泡沫的析液进程和降低析液速率。通过灭火过程的火焰温度测定,发现含醇泡沫作用下10 cm和20 cm高度处的火焰最大降温速率为20.1℃·s^-1和11.2℃·s^-1,相较于无醇泡沫体系降温效果显著,降温增幅分别为39.58%和14.29%。含醇泡沫灭火剂相对于无醇泡沫灭火时间缩短了3.6 s,缩短幅度为37.5%。适量浓度的异丁醇引入到无氟泡沫体系中,可有效延缓泡沫析液进程,提高泡沫体系的发泡倍数及稳泡性能,为无氟泡沫的优化设计提供了一条新路径。建立了基于25%析液时间、平均析液速度、最大降温速率和灭火时间等综合指标的灭火效果考察方法,为泡沫灭火效能的实验室评价提供了参考依据。     

低碳醇改性无氟泡沫的性能分析与扑灭油池火的实验研究

针对现有氟碳类泡沫灭火剂关键组分PFOS因国际环境公约出于环保和健康而限用,以及现有泡沫灭火剂还存在析液速度快而影响灭火能效等问题,在前人及团队探究无氟泡沫复配方案基础上,基于火灾化学理论与表面活性剂技术,遴选碳氢/有机硅表面活性剂(LS-99/SDS)为基剂,通过引入可改善气泡聚并的低碳醇(乙醇、正丙醇和异丁醇)调控泡沫的发泡倍数和25%析液时间等性能,开展含醇泡沫和无醇泡沫的灭火对比实验,考察低碳醇引入后的泡沫灭火能效。结果表明,引入适量浓度低碳醇可显著影响LS-99/SDS复配体系的发泡倍数和25%析液时间。相比乙醇和正丙醇,当异丁醇质量分数为0.1%时,可有效延缓含醇泡沫的析液进程和降低析液速率。通过灭火过程的火焰温度测定,发现含醇泡沫作用下10 cm和20 cm高度处的火焰最大降温速率为20.1℃·s^-1和11.2℃·s^-1,相较于无醇泡沫体系降温效果显著,降温增幅分别为39.58%和14.29%。含醇泡沫灭火剂相对于无醇泡沫灭火时间缩短了3.6 s,缩短幅度为37.5%。适量浓度的异丁醇引入到无氟泡沫体系中,可有效延缓泡沫析液进程,提高泡沫体系的发泡倍数及稳泡性能,为无氟泡沫的优化设计提供了一条新路径。建立了基于25%析液时间、平均析液速度、最大降温速率和灭火时间等综合指标的灭火效果考察方法,为泡沫灭火效能的实验室评价提供了参考依据。     

Aerogel-like ceramic foams with super-high porosity and nanoscale cell wall from sol nanoparticles stabilized foams

Ultralight ceramic foam materials with high porosity play an important role in increasingly hi-tech areas due to the combinative merit of ceramic material and highly porous structure. So far, it remains challenging to fabricate alumina ceramic foams with extremely high porosity and high specific surface area that are comparable to aerogel materials by employing a low cost, eco-friendly and convenient approach. For the first time, we propose the preparation of aerogel-like ceramic foams with nanoscale cell wall and unprecedentedly high porosity using boehmite sol as both ceramic source and bubble interface stabilizer, based on sol nanoparticles stabilized foams using sodium lauryl sulfate (SDS) as modifier. The obtained ultra-stable sol foams allow for the achievement of bulk foams with ultrathin cell wall with thickness in the range of 30-90 nm, super-high porosity up to 99%, and large specific surface area of 280 m²/g, which is attributed to the well-organized assembly of nanoparticles at the liquid/air interfaces. This novel foam material demonstrates excellent adsorption ability for polar volatile organic gases (VOCs) due to its extremely high porosity and large specific surface area.     

Experimental Study on Foam Properties of Mixed Systems of Silicone and Hydrocarbon Surfactants

Silicone surfactants are inevitably involved in industrial applications in combination with hydrocarbon surfactants, but properties of the mixtures of silicone and hydrocarbon surfactants have received little attention, especially foam properties of the mixtures. In this study, aqueous solutions of respective binary mixtures of a nonionic silicone surfactant with anionic, cationic, and nonionic hydrocarbon surfactants were prepared for evaluation of their foam properties. Surface tension of aqueous solutions of the mixtures were measured with the maximum bubble pressure method. Foaming ability and foam stability of the mixtures were then evaluated with the standard Ross–Miles method. The findings show that the addition of the silicone surfactant results in a decrease in surface tension for aqueous solutions of the hydrocarbon surfactants. The critical micelle concentration (CMC) of the hydrocarbon surfactants is also changed by the additive silicone surfactant. Additionally, clear foam synergistic effects were observed in the mixtures of silicone and hydrocarbon surfactants, regardless of the ionic types of the hydrocarbon surfactant. The foam stability of the hydrocarbon surfactant was shown to generally improve with the increasing concentration of the silicone surfactant. Even so, aqueous solutions of different ionic hydrocarbon surfactants in the presence of the silicone surfactant will give different foam stabilities. The results of the present study are meant to provide guidance for the practical application of foams generated by the mixtures of the silicone and hydrocarbon surfactants.     

Coalescence of bubbles and stability of foams in aqueous solutions of Tween surfactants

Coalescence of air bubbles and stability of foams in aqueous solutions of Tween 20, 40, 60 and 80 are reported in this work. Adsorption of the surfactants at air–water interface was studied by measuring the surface tension of the surfactant solutions. The surface tension profiles were fitted using a surface equation of state derived from the Gibbs and Langmuir adsorption equations. The critical micelle concentration and surface tension at this concentration were determined. The effect of surfactant concentration on coalescence of air bubbles at flat air–water interface was studied. The role of steric force on coalescence time was investigated. The coalescence time distributions were fitted by the stochastic model. The mean values of the distributions were compared with the predictions of seven film-drainage models. Stability of foams was analyzed by the Ross–Miles test. The initial and residual foam heights were measured at different surfactant concentrations. The stability of foams was compared with the coalescence time of the bubbles.     

一种新型含十六烷基Gemini表面活性剂的合成及性质研究

以N,N-二甲基乙醇胺（DMAE）、己二酸-qt酯（DMH）和1-溴代十六烷为原料,合成了-种新型含十六烷基Gemini阳离子表面活性剂,总收率67．52％（以己二酸二甲酯计）。产物经1H—NMR、IR和元素分析确定了结构,其熔点为178～180℃,并对表面活性剂的性能进行了讨论。电导法测定产物的CMC（临界胶束浓度）为8．45×10^5mol／L,其乳化力较十二烷基硫酸钠（SDS）强,发泡性和稳泡性不及十二烷基硫酸钠（SDS）。     

消泡剂的选择及其对水性涂料体系的影响

在水性涂料体系的制造及使用过程中，泡沫现象是普遍存在的问题。在这个体系中，泡沫产生及稳定的原因和泡沫的种类已成为广泛研究的课题。泡沫是由于加入一定浓度的表面活性剂而产生的，如在加入过程中能够散布在气／液界面上，使其表面张力下降可达到消泡的目的。本文讨论了泡沫的种类、产生、现象、性质以及具有高性能的消泡剂。