Interaction of cetyltrimethylammonium bromide with cefixime trihydrate drug at different temperatures and compositions: Effect of different electrolytes

Herein,conductivity measurements have been carried out to explore the interaction between cetyltrimethylammonium bromide(CTAB,a cationic surfactant) and antibiotic drug(cefixime trihydrate(CMT)) in water and also in occurrence of inorganic salts(NaCl,Na_2 SO_4 and Na_3 PO_4) over the temperature range of 303.15-323.15 K with an interval of 5 K.In all cases,two critical micelle concentrations(c~*) were achieved for the CMT-surfactant system.Addition of CMT drug to CTAB solution decreases the values of c~*which indicates the interaction between CMT and CTAB.Both values of c~*for CMT-CTAB mixture in the presence of salts are lower in magnitude compared to the aqueous medium which indicates that micellization of the CMT-CTAB mixed system is favorable in salt solution.The values of △G_m~0 were obtained to be negative indicating the spontaneity of the micellization process and the extent of spontaneity further increases by means of rising temperature.The obtained outcomes from the ΔHm0 and ΔSm0 values disclose that the interactions between CMT and CTAB are mostly electrostatic along with hydrophobic in nature.The thermodynamic parameters of transfer and enthalpy-entropy compensation phenomenon were also determined and discussed in detail.     

Interaction of ciprofloxacin hydrochloride with sodium dodecyl sulfate in aqueous/electrolytes solution at different temperatures and compositions

Interactions of ciprofloxacin hydrochloride(CPFH) with sodium dodecyl sulfate(SDS) were investigated by conductivity measurement in H_2O/electrolyte solutions(NaCl, Na_2SO_4 Na_3PO_4) over 298.15–318.15 K temperature range(with 5 K interval) considering the human body temperature. In all cases, two critical micelle concentrations(c~*) were observed which are increased in the presence of drug and decreased in the presence of salts enunciating the presence of interaction amongst the studied components. For(CPFH + SDS) system in the presence of salt, the c~*values at 303.15 K and I = 0.50 mmol·kg~(-1) followed the order: C_(NaCl)C_(Na_2SO_4)C_(Na_3PO_4). The ΔG_(1,m)~0 and Δ G_(2,m)~0values are found to be negative for all systems that show that the micellization process is thermodynamically spontaneous. For(CPFH + SDS) system in water, the Δ H_m~0 Δ S_m~0 values reveal that the micellization processes is both entropy dominated in almost all cases. In the occurrence of electrolytes, Δ H_m~0 and Δ S_m~0 values indicate that micellization processes are both entropy enthalpy restricted at upper temperature but it becomes totally entropy dependent at higher temperature. The higher positive Δ S_m~0 values indicate the enhanced hydrophobic interaction in presence of salts. The enthalpy-entropy compensation was determined from the linear relationship betweenΔ H_m~0 and Δ S_m~0 values in every state. Different transfer energies as well as compensation temperature and intrinsic enthalpy were also evaluated and the behaviors were comparable to other biological system.     

Low-temperature sintering of PZT ceramics

The required sintering temperature of Pb(Zr_0·52Ti_0·48)O₃ ceramics (abbreviated as PZT 52/48) can be lowered to about 1000°C by incorporating Li₂CO₃, Na₂CO₃ or Bi₂O₃. A dielectric constant of about 1000 and a planar coupling factor of between 45% and 65% are obtained in PZT 52/48 ceramics sintered at 1025°C, with added Li₂CO₃ and Bi₂O₃. The optimal amount of the additives, which can be deduced from the densification, the dielectric and piezoelectric properties of the sintered PZT 52/48 ceramics, is 0·375 wt% of Li₂CO₃ together with an equal mole fraction of Bi₂O₃. A planar coupling factor of 65% is obtained. This is explained, with the aid of X-ray diffraction (XRD) analysis, by a maximum c/a ratio and consequently by a large spontaneous polarization. The PZT 52/48 ceramics sintered with Li₂CO₃ and Bi₂O₃ under the optimal conditions can have ε₃₃^T of about 1000, k_p higher than 60%, Q_m around 100 and tan δ less than 2·0%.     

无氟无铵铝合金表面预处理新工艺

针对铝合金表面预处理过程存在污染严重、水耗高等问题,研究开发无氟无铵铝合金表面预处理新工艺。考察了碱性药剂配方组成及浓度、温度和时间对铝耗和铝合金表面形貌的影响,并通过正交实验确定了新工艺的优化方案。研究结果表明,经过“预处理-中和”两个步骤,铝合金表面平整、起砂细腻,铝耗仅为 2.0%。新工艺起砂效果优于传统碱蚀工艺,与传统酸蚀工艺细腻砂面相近。新工艺铝耗比传统碱蚀工艺降低约71%,与传统酸蚀工艺相近。新工艺操作时间比传统碱蚀工艺和酸蚀工艺分别缩短了23%和31%。最佳药剂配方为Na₂CO₃（80 g·L^-1）, NaOH（8 g·L^-1）,Na₂SO₄（25 g·L^-1）, Na₃PO₄（20 g·L^-1）, SDS（0.6 g·L^-1）, 甘油（5 g·L^-1）。 最佳操作条件为55℃和10 min。新工艺不仅从工艺源头消除了氟和氨氮污染,还实现了除油-起砂-去机械纹等多功能一体化集成。具有低污染、低铝耗、低水耗、短流程、高效率等优点,兼具环境友好和资源节约等优势。     

多组分氯盐体系镁锂分离规律初探

以Na₂CO₃为沉淀剂,初步研究了多组分氯盐混合体系（0.6 mol MgCl₂+1.1 mol LiCl+3.2 mol NaCl）中选择性沉镁的工艺规律。结果表明：在25~80 ℃,总C与总Mg物质的量比[n（C_T）/n（Mg_T）]为 0.8~1.1时,25 ℃形成针状MgCO₃·3H₂O,40 ℃以上形成Mg₅（CO₃）₄（OH）₂·4H₂O不规则片状团聚微球,其中40~50 ℃形成的片状物较为分散且粒径较小,导致固液分离困难。40 ℃时沉镁率最低。温度越高,Li₂CO₃越易形成,沉锂率越大。n（C_T）/n（Mg_T）越大沉镁率和沉锂率越高。室温（25 ℃）、n（C_T）/n（Mg_T）=1.0时,沉镁率达98%以上,且沉锂率<0.1%,镁锂分离效果最好。     

Ta、Ba共掺杂石榴石型Li7La3Zr2O12电解质的制备及性能研究

传统锂离子电池采用有机电解液体系,能量密度难以进一步提升,同时存在一定的安全隐患。采用无机固体电解质构建全固态锂电池,在提高电池能量密度同时可兼顾安全性问题。在众多无机固体电解质中,Li₇La₃Zr₂O₁₂(LLZO)石榴石电解质具有离子电导率高、与金属锂接触稳定等优势,成为受人关注的材料。为了进一步提高该材料的导电性,采用固相法合成Ta、Ba共掺杂LLZO(Li_7-x+yLa_3-yBa_yZr_2-xTa_xO₁₂)电解质,采用X射线衍射、扫描电子显微镜和电化学阻抗法分析样品的物相结构、微观形貌及离子电导率。结果表明,Ta⁵⁺掺杂能够稳定立方相结构,Ba²⁺作为掺杂剂和烧结剂,促进晶粒生长和陶瓷致密化,从而降低总电阻。其中,Li_6.45La_2.95Ba_0.05Zr_1.4Ta_0.6O₁₂样品在室温下的总电导率为1.07×10^-3 S·cm^-1,活化能为0.378 eV。Ta⁵⁺/Ba²⁺共掺杂有利于制备高致密度和高电导率的石榴石型电解质材料。     

313.15 K四元体系Na+// S O 4 2 - ， C O 3 2 - ， N O 3 - -H2O固液相平衡研究

采用等温溶解法研究313.15 K下四元体系Na⁺// \mathrm{S} {\mathrm{O}}_4^{2-} , \mathrm{C} {\mathrm{O}}_3^{2-} , \mathrm{N} {\mathrm{O}}_3^{-} -H₂O的固液相平衡关系。测定了平衡溶液的溶解度数据及物理性质数据,包括密度、黏度、折射率。根据实验数据,绘制了相应的干盐相图、水图及物理性质-组成图。实验结果表明：313.15 K下,此四元体系相图包括两个共饱和点,六条单变曲线以及五个单盐结晶区域(分别为NaNO₃,Na₂SO₄,Na₂CO₃·H₂O, Bur(Na₂CO₃·2Na₂SO₄),Da(NaNO₃·Na₂SO₄·H₂O)),其中Bur的结晶区域最大,最容易从混合溶液中结晶析出。实验中的物理性质(黏度、密度、折射率)随J(Na₂SO₄)的变化呈现相似性规律。该体系中存在复盐碱芒硝Bur(Na₂CO₃·2Na₂SO₄)、钠硝矾Da(NaNO₃·Na₂SO₄·H₂O),结晶水合物(Na₂CO₃·H₂O),没有固溶体存在,故该体系是一个复杂的共饱和型。实验所获数据和结论对煤化工过程产生的高盐废水结晶析盐工艺开发及实现资源梯级综合利用具有重要意义。     

Phase Behavior of Sodium Dodecyl Sulfate-n-Butanol-Kerosene-Water Microemulsion System

Experiments were carried out to investigate the influences of cation from electrolytes and acidity/alkalinity on the phase behavior of sodium dodecyl sulfate-n-butanol-organics-water （with electrolytes） microemulsion sys-tem. The organics used is commercial kerosene. The volume ratio of water to organics is 1︰1. The results show that the type and valence of electrolyte cations are important factors influencing the microemulsion behavior. Biva-lent Ca2＋is more effective than monovalent K＋and Na＋for the formation of Winsor type III and II microemulsion. For electrolytes with the same monovalent cation Na＋, i.e. NaCl and Na2CO3, anions in the electrolyte have some effect. Bivalent anion 23CO - leads to a lower activity of cation Na＋than monovalent anion Cl-. NaOH （or KOH） behaves similar with NaCl （or KCl）. When HCl is used as electrolyte, its acidity plays an important role. Phase in-version of microemulsion from type III （or II） to type I is observed through precipitation of Ca2＋using Na2CO3, neutralization of HCl by NaOH, and addition of water to the system, which releases the oil from the microemulsion.     

Effect of electro-chemical properties of sodium salts of various anions on their diffusional parameters in symmetrical cellulose acetate membranes

A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na₂SO₄), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10⁻² for sodium halides and 10⁻³ for Na₂SO₄. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D⁽⁰⁾ are obtained as 0.015–0.03 μm²/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane D_d and in the porous D_p, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to D_d, D_p increases with the increase of W_w and can be correlated as D_p,c = _d exp (γ × W_w). It is shown that the averaged D_d, _D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λ_cation) depends on equivalent ionic conductivity of anion of salt, λ_an.     

脱硝协同汞氧化聚苯硫醚四元催化滤料制备方法及理化特性

采用原位氧化法（ISM）、浸渍煅烧法（ICM）和涂覆法（CM）制备聚苯硫醚（PPS）双效催化滤料,在模拟烟气固定床系统中考察了滤料低温NO_x催化协同Hg⁰氧化性能,深入分析了原位氧化滤料表面形貌、元素分布、晶态结构和Hg及NO_x赋存形态。结果表明：在相同条件下,3种制备方法对应滤料催化活性大小顺序为Mn-Ce-Fe-Co-O_x/PPS@ISM＞Mn-Ce-Fe-Co-O_x/PPS@ICM＞Mn-Ce-Fe-Co-O_x/PPS@CM。ISM对应PPS单层饱和负载量约为0.9,活性反应温度窗口为110~210℃,其中170℃时Mn-Ce-Fe-Co-O_x/PPS@ISM的非均相NO氧化、NO_x还原和Hg⁰氧化效率最高分别达到8.6%、84.6%和93.2%。程序升温脱附实验结果表明：(0.9)Mn-Ce-Fe-Co-O_x/PPS@ ISM表面NO_x吸附活性位点中弱碱位数量占优,而中碱位化学吸附NO主要以NO_y（y=2或3）结构存在,歧化态NO₂次之。同时,Hg与NO在氧气条件下以非均相反应途径转化为HgO和Hg(NO₃)₂/Hg₂(NO₃)₂。表征结果表明：ISM制备的MnO_x、CeO_x、CoO_x和Fe₂O₃复合氧化物呈弱晶相、高度分散团絮状结构赋存于PPS@ISM纤维。     

Na2SO4掺杂含MgO铝酸钙熟料的结构表征及浸出性能

使用分析纯MgO、CaCO₃、SiO₂、Al₂O₃与Na₂SO₄在1350℃保温1 h合成了掺杂Na₂SO₄的含MgO铝酸钙熟料,在Na₂CO₃溶液体系下研究了其氧化铝浸出性能,通过XRD等分析手段对其晶体结构和自粉化性能进行了研究。结果表明,Na₂SO₄可以显著提升铝酸钙熟料的浸出性能,Na₂SO₄掺杂量由0%提高到4%,熟料的氧化铝浸出率由61.89%提高到92.01%,继续添加Na₂SO₄,浸出性能趋于稳定。由XRD结果可知,Na₂SO₄促使20CaO·13Al₂O₃·3MgO·3SiO₂（Q相）发生分解并使其转变为12CaO·7Al₂O₃（C₁₂A₇）。Na⁺进入C₁₂A₇晶格引起晶格畸变,从而提高C₁₂A₇的氧化铝浸出性能。Na₂SO₄的加入降低了熟料的自粉化性能,Na₂SO₄掺杂量由0%提高到6%,熟料的自粉率由97.46%下降到85.34%,当Na₂SO₄掺杂量达到10%后,熟料自粉率仅为36.3%。     

Fabrication and thermoelectric properties of heavily rare-earth metal-doped SrO(SrTiO3)n (n = 1, 2) ceramics

To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S²σTκ⁻¹) of Ruddlesden–Popper phase SrO(SrTiO₃)_n (or Sr_n+1Ti_nO_3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr_1−xRE_x)_n+1Ti_nO_3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr_1−xRE_x)_n+1 Ti_nO_3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La³⁺ and Nd³⁺ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO₃. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr_0.95La_0.05)₃Ti₂O₇.     

Estimation of the contribution of tube renewal in the terminal relaxation of linear polybutadiene

A set of low-molecular-weight (low-MW) entangled linear polybutadienes with molecular weights between 1.1 × 10⁴ and 2.5 × 10⁵ have been dilutedly embedded in a high-molecular-weight linear polybutadiene (M_w = 7.6 · 10⁵) matrix. The viscoelastic properties of these blends with 9.1% low-MW polymer have been measured. The loss moduli-frequency master curves, G^″ (Щ), contain contributions from both polymers. The contribution of the low-MW polymer is obtained by subtracting the contribution of the matrix. The maximum in G^″, G^″_m, due to the low-MW polymer occurs at a lower frequency (0.3 to 0.5 log units) than in the homopolymer. This result indicates that the longest relaxation time of the entangled linear polymer embedded in a high-molecular-weight matrix is increased by a factor of 2.0 to 3.0 because tube renewal normally operating in the homopolymer is almost completely absent in the matrix. The longest relaxation time of the polymers in the matrix depends on M^3.3₀. This is only slightly less than the dependence found in linear polymer melts (M^3.3₇). This indicates that reptation and chain-end fluctuation together contribute to the relaxation of linear polymers in permanent networks.     

Insight into SO2 poisoning and regeneration of one-pot synthesized Cu-SSZ-13 catalyst for selective reduction of NOx by NH3

The effects of SO₂ on an one-pot synthesized Cu-SSZ-13 catalyst for selective reduction of NO_x by NH₃ were examined. The addition of SO₂ inhibited NO_x conversion significantly below 300 ℃, while no effect on NO_x conversion was observed above 300 ℃. TGA, TPD, and XPS results showed that the deactivation was caused by the formation of (NH₄)₂SO₄, SO₂ chemisorption on the isolated Cu²⁺ ion sites, as well as the formation of CuSO₄-like species. Among them, the site-blocking effect of (NH₄)₂SO₄ on Cu²⁺ was the primary reason for deactivation. Fortunately, 89% of deNO_x activity of the poisoned catalyst was recovered after thermal treatment at 500 ℃ in air, where (NH₄)₂SO₄ was completely decomposed. The activity was further recovered with regeneration temperature increasing to 600 ℃, removing the adsorbed SO₂ on the Cu²⁺ sites. The regeneration at 600 ℃ could not recover the activity completely, because of the high stability of CuSO₄-like species.     

Na2CO3基吸附剂颗粒制备及其脱碳性能

采用挤压-滚圆法制备Na₂CO₃基CO₂吸附剂微球颗粒,在自行设计的CO₂吸收系统中对制备的样品进行脱碳性能测试。结合相关表征测试,探明不同载体、不同负载量的Na₂CO₃基吸附剂的微观结构、脱碳性能以及机械性能的变化规律和内在原因。研究表明：不同载体的Na₂CO₃基吸附剂颗粒脱碳性能存在明显差异,其中氧化铝负载的吸附剂（Na₂CO₃/Al₂O₃）的脱碳性能最好,可达1.14mmol/g。铝酸钙水泥负载的吸附剂（Na₂CO₃/CA）机械性能较好,但其脱碳性能最差。结合吸附剂脱碳和机械性能的综合考量,Na₂CO₃/Al₂O₃是最为合适的CO₂吸附剂,并进一步研究不同Na₂CO₃负载量的影响。研究发现随着Na₂CO₃负载量的变化,吸附剂的微观结构、脱碳性能以及机械性能都存在明显的差异。虽然60%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒的机械性能和脱碳效果较好,但其成球度较差,影响其实际应用。质量分数40%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒具有良好的脱碳性能、机械性能以及成球度,CO₂脱除量为1.36mmol/g。总体而言,利用挤压-滚圆法制备的Na₂CO₃基吸附剂颗粒具有良好的流动特性、脱碳性能和机械性能,适用于电厂烟气中的CO₂脱除。     

四元体系NaCl+NaBO2+Na2CO3+H2O 298.15 K 相平衡研究

柴达木盐湖中具有丰富的盐湖离子,对其中的一个四元体系水盐相图开展研究,采用等温溶解平衡法开展了298.15 K时四元体系NaCl+NaBO₂+Na₂CO₃+H₂O相平衡研究,测定了体系平衡液相组成及密度和折光率,绘制了四元体系NaCl+NaBO₂+Na₂CO₃+H₂O 298.15 K的相图及相应的物化性质图。研究发现NaCl+NaBO₂+Na₂CO₃+H₂O四元体系298.15 K 时包含2个共饱点（E₁、E₂）、5条溶解度曲线（AE₁、BE₁、CE₂、DE₂、E₁E₂）、4个结晶区（NaCl、NaBO₂·4H₂O、Na₂CO₃·7H₂O、NaCl·NaBO₂·2H₂O）。其中三元体系NaCl+NaBO₂+H₂O在298.15 K下产生了复盐NaCl·NaBO₂·2H₂O,通过研究发现该四元体系NaCl+NaBO₂+Na₂CO₃+H₂O在298.15 K下也具有NaCl·NaBO₂·2H₂O复盐区。     

Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

固相法制备掺杂型高色度CoxM1-xAl2O4/高岭土复合颜料

为了制备低成本、高色度的钴蓝颜料,本文以高岭土为载体,以Al₂O₃和Co₃O₄为主要原料,通过引入ZnO、CaO及MgO不同金属氧化物,采用固相法制备了高色度(Co_xM_1-xAl₂O₄)/高岭土复合颜料(M为Ca²⁺、Mg²⁺或Zn²⁺)。系统考察了研磨时间、煅烧温度、煅烧时间和不同金属氧化物掺量对复合颜料呈色性能的影响规律。研究表明,在煅烧温度1 200 ℃、研磨时间12 h和n(Co²⁺)/n(M²⁺)为3:2时,制得的复合颜料具有最好的呈色性能(L^*=53.68,a^*=7.58,b^*=-62.89)。同时,引入不同的金属元素,可实现对复合颜料颜色的调控,引入Ca²⁺后,所制备的Co_xCa_1-xAl₂O₄复合颜料偏红相,而引入Zn²⁺后,所制备的Co_xZn_1-xAl₂O₄复合颜料偏绿相。通过相关表征,提出了复合颜料的呈色机理,在颜料制备过程中,引入与Co²⁺离子半径接近的Mg²⁺或Zn²⁺,Mg²⁺或Zn²⁺可进入CoAl₂O₄的四面体配位中,部分替代Co²⁺,形成MgAl₂O₄-CoAl₂O₄或ZnAl₂O₄-CoAl₂O₄的固溶体,而引入离子半径较大的Ca²⁺,形成CaAl₂O₄和CoAl₂O₄的均相混合物。最后,将制得复合颜料应用到有机硅耐热涂料中,可以明显提高有机硅涂料的热稳定性。     

废钒钛系脱硝催化剂碱法回收研究进展

废钒钛系脱硝催化剂属于HW50危险废物,富含V、W/Mo和Ti战略金属资源,具有污染性和资源性的双重特性,对其进行回收具有重要的经济价值和环境效益。碱法回收是当前的主流回收工艺。本文主要总结了废钒钛系脱硝催化剂碱浸法和碱焙烧法回收的研究进展,重点分析了采用NaOH、NH₄OH、(NH₄)₂CO₃等碱性溶液浸出以及采用NaOH、Na₂CO₃、CaO等碱性化合物焙烧提取工艺参数及对其中有价金属元素的回收效果。针对当前碱法工艺存在的碱耗量大、能耗高、废液产生量大、污染严重等相应问题,提出了进一步关注点应集中于阐明多种碱性物质之间的协同作用,通过混合碱的耦合反应提升回收效果。本文对降低废钒钛系脱硝催化剂回收能耗,提升碱性化合物利用率和回收产品质量具有良好的指导意义。     

Electrochemical beaviour of the solid ionic conductor Ag7I4PO4

Electrochemical investigation of the solid superionic conductor Ag₇I₄PO₄ (0.8 AgI + 0.2 Ag₃PO₄) at room temperature and at 40°C were performed by means of cyclic voltammetry, cyclic chronoamperometry and cyclic chronocoulometry, normal pulse polarography and ac polarography. It was shown that the Ag⁺ ↔ Ag redox process on Pt and Ag working electrode occurs with a certain overvoltage, ie that for Ag⁺ → Ag⁺ oxidation and the return of Ag⁺ ions into the electrolyte a certain overvoltage is necessary. From the determined values of the exchange current one estimates the redox process as a rather fast one. The silver working electrode is electrochemically inactive, while only cathodically deposited silver is electrochemically active and can be oxidized to Ag⁺ ions. Chronoamperometry and chronocoulometry show that there is a certain difference in the behaviour of Pt and Ag working electrodes due to uneven passivating anodic processes. On the basis of measurements of faradaic and capacitance currents and their dependence on frequency, diagrams of complex impedance of the Pt/Ag₇I₄PO₄ interface at various anodic and cathodic polarizations of the Pt electrode were plotted. The dependence of the serial capacity of the interface on the dc potential and temperature are discussed.