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New magnesium intermetallic compounds are promising, reliable, reversible hydrogen accumulators 新型镁金属间化合物是有前途的、可靠的、可逆的储氢剂
Pub Date : 2023-09-30 DOI: 10.15407/hftp14.03.415
Z. Matysina, A. Zolotarenko, O. Zolotarenko, N. Shvachko, N. Akhanova, M. Ualkhanova, D. V. Schur, M. Gabdullin, Yuriy I. Zhirko, E. Rudakova, Yuriy O. Tarasenko, A. Zolotarenko, M. Chymbai, O. Havryliuk
The proposed work considers: hydrogen sorption properties of systems of magnesium intermetallic compounds with a complex cubic structure C15b, as promising, reliable, reversible hydrogen accumulators. Considered thermal processes. A statistical theory is proposed for the cubic structure C15b of composition MgRT4Hx, where R = Ce, La, Nd, Pr, Y; T = Co, Ni; 0 ≤ x ≤ 6 at phase transitions in the process of hydrogenation, taking into account pressure. The concentration dependences of the maximum values of the order parameter and a priori probabilities are established. Hydrogen solubility isopleths and isotherms are calculated and considered, and a graphical concentration dependence of the hydrogen atom ordering temperature in MgCeCo4-type crystals is created. The order-disorder transition is considered with allowance for temperature, and the process of absorption-desorption of hydrogen by the C15b structure is also studied. The equation of thermodynamic equilibrium with the calculation of free energy is derived. And also considered the graphical dependence of the value of the order parameter on temperature and pressure. The temperature dependence of hydrogen solubility in the α, β phases for the MgCeCo4 crystal is considered. The configurational heat capacity of a crystal of the MgSnCu4Hx type structure has been studied, taking into account the temperature and the order parameter. A graph of hydrogen absorption-desorption of the MgCeCo4Hx crystal has been constructed. A comparative analysis of the experimental and practical results of the absorption-desorption of hydrogen by the working fluid of the composition MgRT4Hx has been carried out.
本文研究了具有复杂立方结构C15b的镁金属间化合物体系的吸氢性能,作为一种有前途的、可靠的、可逆的储氢器。考虑热过程。提出了MgRT4Hx的立方结构C15b的统计理论,其中R = Ce, La, Nd, Pr, Y;T = Co, Ni;考虑压力,加氢过程相变时0≤x≤6。建立了阶参数最大值和先验概率的浓度依赖关系。计算并考虑了mgceco4型晶体中氢原子溶解度等容线和等温线,并建立了氢原子有序温度的浓度依赖图。考虑了温度条件下的有序-无序转变,研究了C15b结构对氢的吸附-解吸过程。导出了计算自由能的热力学平衡方程。并考虑了序参量值对温度和压力的图形依赖性。研究了MgCeCo4晶体α、β相氢溶解度的温度依赖性。研究了考虑温度和序参量的MgSnCu4Hx型晶体的组态热容。构造了MgCeCo4Hx晶体的吸氢-解吸图。对MgRT4Hx组份工质吸解吸氢的实验结果与实际结果进行了对比分析。
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引用次数: 0
Formation and stability of gold nanoparticles in colloids prepared by citrate method 柠檬酸盐法制备胶体金纳米颗粒的形成及稳定性
Pub Date : 2023-09-30 DOI: 10.15407/hftp14.03.310
N. Vityuk, A. Eremenko, N. Rusinchuk, V. Lozovski, M. Lokshyn, V. Lysenko, I. Mukha
Gold nanoparticles (Au NPs) have found a variety of applications in different areas, particularly in biomedical practices. The activity of Au NPs strongly depends on the size and association of particles in colloid, that in turn are greatly affected by experimental parameters of the reaction. The obtaining of Au NPs even via classical procedure of citrate method can be a challenge. In the present work we applied different experimental approaches to affect the process of Au NPs formation in the presence of sodium citrate. Au NPs were obtained using different experimental procedures and varying the ratio of reagents, their concentrations, temperature of reaction, duration of heating, the order of introduction of reagents into the reaction mixture, pH, and so on. Comparative analyses of UV-vis spectra with DLS data by number, volume and intensity basis allowed to trace the changes in Au NPs colloid, find optimal experimental conditions and predict prolonged stability of colloids. Applying size-dependent Hamaker constant to DLVO theory explains experimental results. The formation of Au NPs strongly depends on the ratio of the functional groups of the molecule involved simultaneously in the reduction of metal ions, the binding to the surface of Au NPs and the formation of a charge for stabilization due to electrostatic repulsion. The change in the ratio of components is not enough to get a different size of Au NPs. Big concentration of the reagents mostly affects the aggregation process and colloid aging. Temperature is a critical activation factor, that should be about 100 °C, but prolonged heating causes collision induced aggregation. The initial stage of particles growth (the mechanism) can be affected with the change of pH of the system due to formation of deprotonated carboxyl groups and gold hydroxocomplexes.
金纳米颗粒(Au NPs)在不同领域,特别是在生物医学实践中有各种各样的应用。Au NPs的活性很大程度上取决于胶体中颗粒的大小和结合体,而这些又受到反应的实验参数的很大影响。即使通过经典的柠檬酸盐法也很难得到Au NPs。在目前的工作中,我们采用不同的实验方法来影响金NPs在柠檬酸钠存在下的形成过程。采用不同的实验方法,通过改变试剂的比例、浓度、反应温度、加热时间、将试剂引入反应混合物的顺序、pH等,得到金纳米粒子。紫外-可见光谱与DLS数据在数量、体积和强度基础上的对比分析,可以追踪Au NPs胶体的变化,找到最佳的实验条件,预测胶体的长期稳定性。将大小相关的Hamaker常数应用于DLVO理论,解释了实验结果。Au NPs的形成强烈依赖于同时参与金属离子还原的分子官能团的比例,与Au NPs表面的结合以及由于静电排斥而形成的稳定电荷。组分比例的变化不足以得到不同尺寸的Au NPs。大浓度的试剂主要影响胶体的聚集过程和老化。温度是一个关键的激活因素,应该在100°C左右,但长时间加热会导致碰撞诱导聚集。由于去质子化羧基和金羟基配合物的形成,pH的变化会影响颗粒生长的初始阶段(机理)。
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引用次数: 0
Research of toxic behavior of copper nanoparticles: effect on electrosurface and biochemical parameters of bacterial cells 铜纳米颗粒毒性行为的研究:对细菌细胞电表面和生化参数的影响
Pub Date : 2023-09-30 DOI: 10.15407/hftp14.03.372
T. Gruzina, L. Rieznichenko, L. Yakubenko, V. I. Podolska, N. I. Grishchenko, Z. Ulberg, S. Dybkova
This research is aimed at the investigation the electrosurface and biochemical parameters of bacterial cells B. cereus B4368, L. plantarum, E. coli K-A, P. fluorescens B5040 under the influence of copper in ionic form and as nanoparticles in order to determine the nature and level of their toxic effect on bacteria. Copper nanoparticles synthesized in aqueous solution with NaBH4 and stabilized with dextran were used. Changes in membrane transport parameters were assessed by the value of ATPase activity; changes in transmembrane potential were assessed by the method of penetrating tetraphenylphosphonium cations (TPP+); and bacterial integrity was assessed by UV spectroscopy of cellular metabolites. A concentration-dependent inhibition of the membrane ATPase reaction and dissipation of the transmembrane potential under the action of both forms of copper was found, and the inhibitory effect in the case of the nanoparticles was on average 20 % higher than in the ionic form. As a result of heterocoagulation of dextran-stabilized copper nanoparticles and bacteria, a decrease in the negative ξ - potential of bacteria was observed, which was 40 % more effective under the action of copper nanoparticles compared to Cu2+ ions. The most significant changes in membrane parameters were observed in the range 10–60 μM of copper concentrations. With B. cereus B4368 cells taken as an example, we found a violation of the barrier function of their cell membrane under the influence of both copper preparations. In the case of copper nanoparticles, nucleic acid leakage from the bacterial cytoplasm was detected, which was confirmed by the absorption band at 260 nm. The results obtained indicate a high level of sensitivity of the studied electrosurface and biochemical parameters of bacterial cells to the effects of ionic and nanoparticle copper, which allows them to be used as indicators of the toxicity of metal nanoparticles in the development of metal-containing probiotic preparations.
本研究旨在研究离子铜和纳米铜对蜡样芽孢杆菌B4368、植物乳杆菌、大肠杆菌K-A、荧光杆菌B5040等细菌细胞的电表面和生化参数的影响,以确定它们对细菌的毒性作用的性质和水平。用NaBH4在水溶液中合成铜纳米粒子,用右旋糖酐稳定。通过atp酶活性值评估膜运输参数的变化;采用穿透四苯基磷离子(TPP+)法测定跨膜电位的变化;并用紫外光谱法测定细胞代谢物的细菌完整性。在两种形式的铜的作用下,膜atp酶反应和跨膜电位的耗散都有浓度依赖性的抑制,并且纳米粒子的抑制效果比离子形式的平均高20%。由于右旋糖酐稳定的铜纳米粒子与细菌的异凝聚作用,观察到细菌的负ξ电位下降,与Cu2+离子相比,铜纳米粒子的作用效率提高了40%。铜浓度在10 ~ 60 μM范围内,膜参数变化最为显著。以蜡样芽孢杆菌B4368细胞为例,我们发现两种铜的制备都破坏了其细胞膜的屏障功能。在铜纳米粒子的情况下,检测到核酸从细菌细胞质中泄漏,并通过260 nm的吸收带证实了这一点。结果表明,所研究的细菌细胞的电表面和生化参数对离子铜和纳米铜的影响具有很高的敏感性,这使得它们可以作为金属纳米颗粒毒性的指标,用于含金属益生菌制剂的开发。
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引用次数: 0
Targeted requirements for biomedical nanomaterials based on dispersed oxides and textiles modified with metal NPS 基于分散氧化物的生物医学纳米材料和用金属NPS改性的纺织品的目标要求
Pub Date : 2023-09-30 DOI: 10.15407/hftp14.03.300
A. Eremenko, I. Petrik, A. Rudenko
This article analyses some literature data and the authors’ developments in the technology of creating of therapeutic depots in the form of films, dispersions of metal oxides and textiles with immobilized biocompatible silver nanoparticles (NPs) in the structure of SiO2, TiO2, cotton, biopolymers (alginate, chitosan, lignin, etc.), that have biocidal action, and future trends in this area. We and other researchers have developed methods for the synthesis of photocatalytically active TiO2 and SiO2 films, modified with gold/silver/copper NPs, suitable for medical use. An economical and simple low-temperature methods of manufacturing antimicrobial textiles by photo- or thermal activation and the possibility of their multiple use have been developed. The production of biomedical textiles is recently focused on the widespread use of non-toxic biopolymers, combined with textile. We have obtained compositions based on nanodispersed silica with polysaccharide sodium alginate and silver NPs with pronounced hemostatic and bactericidal properties. Obtaining a hybrid material based on a bactericidal textile combined with a dispersed oxide is promising for additional absorption of toxins and wound cleaning. The creation of such universal multifunctional materials includes their high bactericidal and antiviral multiply use. Hybrid materials based on metal NPs in the structure of carriers of different nature as films and dispersions of biocompatible oxides, biopolymers, textiles have a protection against possible toxic effects of nanoparticles and metal ions, self-cleaning capability, photocatalytic, hemostatic properties, temperature resistance, and other. The development and application of such materials is growing rapidly. So, materials based on Ag/SiO2 dispersions have high antibacterial and antiviral action (single application). Ag/SiO2 films can act as durable antibacterial cover. There is an enhancement in the antibacterial properties of Ag-TiO2 NPs under visible light irradiation and the photocatalytic effect under UV light (single application in the powder form). Self-cleaning, antimicrobial and UV-protective properties have Ag-TiO2 NPs in textile. Cotton modified with MeNPs demonstrates high efficiency of destruction of bacteria E. coli, K. pneumoniae, E. aerogenes, P. vulgaris, S. aureus, C. albicans, etc., with saving of biocidal activity after 5 cycles of washing. The dynamics of silver ions release from the surface of NPs in the structure of textile upon their contact with water for 72 hours have been studied. The number of irreversibly bound particles in textile structure is sufficient for subsequent use. Modified fabrics are reusable. Composites based on metal NPs in the structure of silica or titania in the presence of biopolymers are effective hemostatic agents with a bactericidal effect. Sodium alginate has a reducing and stabilizing effect on nanoparticles, and silica prevents agglomeration of metal NPs in the resulting composite. However, i
本文分析了一些文献资料和作者在二氧化硅、二氧化钛、棉花、生物聚合物(海藻酸盐、壳聚糖、木质素等)结构的固定化生物相容性银纳米粒子(NPs)以膜、金属氧化物分散体和纺织品的形式创建具有生物杀灭作用的治疗库的技术进展,并展望了该领域的发展趋势。我们和其他研究人员已经开发了合成光催化活性TiO2和SiO2薄膜的方法,用金/银/铜NPs修饰,适用于医疗用途。提出了一种经济简便的低温光活化或热活化抗菌纺织品的制备方法,并探讨了其多种用途的可能性。近年来,生物医用纺织品的生产重点是广泛使用无毒生物聚合物与纺织品相结合。我们已经获得了基于纳米分散二氧化硅与多糖海藻酸钠和银NPs的组合物,具有明显的止血和杀菌性能。获得一种基于杀菌纺织品和分散氧化物的混合材料,有望用于额外的毒素吸收和伤口清洁。这种通用多功能材料的创造包括其高杀菌和抗病毒的多重用途。以不同性质载体结构的金属NPs为基础的杂化材料,如生物相容性氧化物、生物聚合物、纺织品的薄膜和分散体,具有防止纳米颗粒和金属离子可能产生的毒性作用、自清洁能力、光催化、止血性能、耐温性能等。这类材料的开发和应用正在迅速发展。因此,基于Ag/SiO2分散体的材料具有很高的抗菌和抗病毒作用(单次应用)。Ag/SiO2薄膜可作为耐用的抗菌膜。Ag-TiO2 NPs在可见光照射下抗菌性能增强,在紫外光下光催化效果增强(单次以粉末形式应用)。Ag-TiO2纳米粒子具有自清洁、抗菌和防紫外线等性能。经MeNPs改性的棉花对大肠杆菌、肺炎克雷伯菌、产气大肠杆菌、寻常假单胞菌、金黄色葡萄球菌、白色念珠菌等细菌的杀灭效果较好,洗涤5次后杀灭活性有所降低。本文研究了织物结构中NPs表面与水接触72小时后银离子的释放动力学。织物结构中不可逆结合颗粒的数量足以供后续使用。修改后的织物可重复使用。在生物聚合物存在下,基于二氧化硅或二氧化钛结构的金属NPs的复合材料是具有杀菌作用的有效止血剂。海藻酸钠对纳米粒子具有还原和稳定作用,二氧化硅可以防止金属纳米粒子在合成的复合材料中团聚。然而,要满足基于分散氧化物组成的金属NPs以及纺织品和/或生物聚合物(“一体化”)的生物医学纳米材料的众多目标要求,以获得一种在使用过程中不会失去其性能的通用多功能材料,是相当困难的。更有意义的是为目标应用生产复合材料,如杀菌和抗病毒,实验室表面的疏水涂层,包装等。这方面的研究正在进行中。
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引用次数: 0
Hong-Ou-Mandel quantum effect on “expanded graphite - cnts” composites 膨胀石墨-碳纳米管复合材料的Hong-Ou-Mandel量子效应
Pub Date : 2023-09-30 DOI: 10.15407/hftp14.03.387
L. Karachevtseva, M. Kartel, Y. Sementsov, O. Lytvynenko, O. Sapelnikova
We investigated influence of multiwalled carbon nanotubes (CNTs) on spectral characteristics of composites “thermo-expanded graphite – carbon nanotubes (TEG–CNTs)”. The introduction of CNTs in an amount of 0-3% by weight of TEG composites results in a significant increase in the strength characteristics and thermal stability of the composites. This result indicates that CNTs is ideal filler for composites based on TEG compositions and structures. Measurements the giant two-polar oscillations with very small half-width 0.5 cm–1 testify the strong interaction of surface polaritons with photons. When frequencies of local oscillations of surface bonds of carbon nanotubes and modes along “nanotube-TEG” boundaries matches, then the light absorption increases 102–105 times. Thus, IR absorption with two-polar oscillations was measured at 0% of nanotubes in TEG at frequency of 2750 cm–1. It is own optical mode in the thermally expanded graphite. 5 peaks with two-polar oscillations were measured in the IR absorption spectra at 1% of carbon nanotubes. And 8 peaks with two-polar oscillations were measured at 3 % of carbon nanotubes at optical mode frequencies along the boundaries of thermally expanded graphite - carbon nanotubes. When frequencies of local oscillations of carbon nanotubes and composite’s modes matches, then the light absorption extremely increases (in 102–105 times), and two-polar IR absorption oscillations with negative components are formed. In general, two-photon interference is a result of quantum entanglement of dipole-active oscillations and splitting of photons according to the Hong-Ou-Mendel (HOM) quantum effect. Two-photon entanglement is built on the basis of the most entanglement states, also known as Bell's states. The HOM–quantum effect on composites “expanded graphite-carbon nanotubes” is promising for the development of highly coherent optical quantum computers.
研究了多壁碳纳米管(CNTs)对热膨胀石墨-碳纳米管(TEG-CNTs)复合材料光谱特性的影响。在TEG复合材料中加入0-3%重量的CNTs,可显著提高复合材料的强度特性和热稳定性。这一结果表明,CNTs是基于TEG组成和结构的复合材料的理想填料。对半宽0.5 cm-1的巨大两极振荡的测量证明了表面极化子与光子的强相互作用。当碳纳米管表面键的局部振荡频率与“纳米管- teg”边界上的模式相匹配时,光吸收增加102 ~ 105倍。因此,在频率为2750 cm-1的TEG中,在0%纳米管的情况下,测量了双极性振荡的红外吸收。它在热膨胀石墨中具有自己的光学模式。在1%碳纳米管的红外吸收光谱中测得5个极性振荡峰。在热膨胀石墨-碳纳米管的边界上,在光学模式频率下,在3%的碳纳米管中测量到8个具有极性振荡的峰。当碳纳米管的局部振荡频率与复合材料的模态相匹配时,光吸收急剧增加(在102 ~ 105倍之间),形成负分量的极性红外吸收振荡。一般来说,双光子干涉是由偶极子主动振荡和光子分裂的量子纠缠引起的,根据Hong-Ou-Mendel (HOM)量子效应。双光子纠缠建立在大多数纠缠态的基础上,也被称为贝尔态。复合材料“膨胀石墨-碳纳米管”上的homo量子效应为高相干光学量子计算机的发展提供了前景。
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引用次数: 0
The antiviral activity of cerium and lanthanum nanooxides modified with silver 银修饰的铈和镧纳米氧化物的抗病毒活性
Pub Date : 2023-06-30 DOI: 10.15407/hftp14.02.262
M. Zahornyi, O. Lavrynenko, O. Pavlenko, O. Povnitsa, L. Artiukh, K. Naumenko, S. Zahorodnia, A. Ievtushenko
Today, the antiviral activity of oxide nanomaterials can be used in the fight against the viral disease COVID-19. It is thought that Ag nanoparticles may bind to the surface glycoprotein of the virus and interfere with the virus’s interaction with epithelial cells, and inhibit virus reproduction by releasing silver ions in the cell. The viruses’ inhibition with RNA (ribonucleic acid) and DNA (deoxyribonucleic acid) genomes by oxide nanocomposites action was presented. In this research, the surface structure of doped CeO2 (La2O3) was studied by nitrogen adsorption-desorption based on BET method. The silver atom’s existence in CeO2 - Ag0 can facilitate the transport of more holes to the surface and can enhance the optical, antivirus activity. The primary particle size of pure cerium dioxide is 7 nm, for CeO2 - Ag composite at 2 and 4 wt. % of silver is 6.5 and 6.9 nm; for La2O3 - Ag 27 and 35 nm, respectively. Cell viability was assessed using an MTT (3-(4,5-Dimethylthiazol 2-yl)-2,5-diphenyltetrazolium bromide) assay after NPs (nanoparticles) exposure, since only viable cells have functional mitochondrial dehydrogenase enzymes that can reduce MTT to formazan. Nanoparticles were non-toxic for BHK-21(Syrian hamster kidney), Hep-2 (Human larynx carcinoma), and MDCK (Canine kidney) cells in concentrations of 10 and 100 μg/ml, while cell viability was within 76÷100 %. La2O3 and CeO2, which contained 4 wt. % of Ag at a concentration of 1000 μg/ml had a lower toxic effect: for BHK-21 cells 68 and 76 % of viable cells, respectively; for Hep-2 - 40 and 36 %, for MDCK - 42 and 48 %; La2O3 and CeO2 with 2 and 5 wt. % of Ag at a concentration of 1000 µg/ml were highly toxic. The level of ВНК-21, Нер-2, and MDCK cells viability was in a range of 7 to 37 %. It has been stated that oxides of cerium and lanthanum have a pronounced virucidal action against the Herpes simplex virus and Influenza A virus by completely inhibiting the development of its cytopathic action. The lanthanum and cerium oxides with 2 and 5 wt. % of silver inhibited the development of the virus’s CPE by more than 5.0 log10 compared to the virus control. The results show that lanthanum and cerium oxides with 2 and 5 wt. % silver have a high virucidal effect against herpes simplex virus type 1. A 1.0÷4.0 log10 reduction in the infectious titer of the Herpes virus synthesized “de novo” in the presence of lanthanum and cerium oxide nanocomposites has been shown.
如今,氧化物纳米材料的抗病毒活性可用于对抗病毒性疾病COVID-19。认为银纳米颗粒可能与病毒表面糖蛋白结合,干扰病毒与上皮细胞的相互作用,并通过在细胞内释放银离子抑制病毒繁殖。本文报道了氧化纳米复合材料对病毒RNA(核糖核酸)和DNA(脱氧核糖核酸)基因组的抑制作用。本研究采用BET法对掺杂CeO2 (La2O3)的氮吸附-解吸进行了表面结构研究。银原子在CeO2 - Ag0中的存在有利于将更多的空穴输送到表面,增强了其光学抗病毒活性。纯二氧化铈的初始粒径为7 nm, 2和4 wt %的CeO2 - Ag复合材料的初始粒径为6.5和6.9 nm;La2O3 - Ag分别为27 nm和35 nm。在NPs(纳米颗粒)暴露后,使用MTT(3-(4,5-二甲基噻唑2-基)-2,5-二苯基溴化四唑)测定法评估细胞活力,因为只有活的细胞才具有功能性线粒体脱氢酶,可以将MTT还原为甲醛。纳米颗粒在浓度为10和100 μg/ml时对BHK-21(叙利亚仓鼠肾)、Hep-2(人喉癌)和MDCK(犬肾)细胞无毒,细胞存活率在76÷100 %以内。在浓度为1000 μg/ml时,Ag含量为4 wt. %的La2O3和CeO2对BHK-21细胞的毒性作用较低,分别为68%和76%;Hep-2 - 40和36%,MDCK - 42和48%;在浓度为1000µg/ml时,La2O3和CeO2分别含2和5 wt. %的Ag呈高毒性。ВНК-21、Нер-2和MDCK细胞活力水平在7% ~ 37%之间。铈和镧的氧化物对单纯疱疹病毒和甲型流感病毒有明显的杀病毒作用,完全抑制其细胞病变作用的发展。与病毒对照相比,含2 wt. %和5 wt. %银的镧和铈氧化物对病毒CPE的抑制作用大于5.0 log10。结果表明,含2和5 wt. %银的镧和铈氧化物对1型单纯疱疹病毒有很强的杀病毒作用。研究表明,在镧和氧化铈纳米复合材料的存在下,疱疹病毒“从头”合成的感染性滴度降低1.0÷4.0 log10。
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引用次数: 0
Mechanical exfoliation of graphite to graphene in polyvinylpyrrolidone aqueous solution 石墨在聚乙烯吡咯烷酮水溶液中机械剥落成石墨烯
Pub Date : 2023-06-30 DOI: 10.15407/hftp14.02.230
L. Myroniuk, D. Myroniuk, E. Maistruk, S. Kuryshchuk, A. Ievtushenko, I. M. Danylenko, V. Strelchuk, I. Koziarskyi
In presented work we have reported that polyvinylpyrrolidone (PVP) is suitable organic solvent for mechanical exfoliation of crystalline graphite to graphene in aqueous solution through kitchen blender technique. Morphological, structural and optical, properties of graphene samples were characterized by scanning electron microscopy, Raman scattering and UV-Visible spectroscopy. Scanning electron microscopy demonstrates folded morphology of graphene flakes with ~4 nm thickness. Raman scattering was revealed the high-quality graphene with low levels of defects after the exfoliation process of graphite/PVP dispersions. The G band at ~1582 cm−1 on Raman spectra is related with stretching vibrations of carbon atoms. The broadening of the G band is not observed, that indicated on absence of the basal plane defects in the graphene structure, which can be introduced during exfoliation by the kitchen blender. The ratio of the intensity of 2D and G bands equal to 1.66 (I2D/IG>1) and the value of 2D band full width at half maximum is 79.88 cm–1, indicated a few-layer graphene (FLG) structure. The defects quantity identified by the intensity ratio of the D and G bands, ID/IG is 0.18, significantly lower than that reported for graphene oxide with basal plane defects (> 1) and for sonication dispersed graphene (~ 0.6). The graphene dispersions were characterized by UV–Vis spectroscopy, minimum transmittance observed at around 270 nm is attributed to the π→π* transitions of aromatic C–C bonds in graphene. The optical transmittance minimum and the overall high transmittance decreasing values observed between 270 and 800 nm strongly suggest the presence of two-dimensional material in the dispersion, thus confirming the successful exfoliation of graphite to graphene by blending. We demonstrate the simple and nontoxic method to product high-quality FLG sheets, free from defects, using a kitchen blender and eco-friendly polyvinylpyrrolidone as an organic exfoliant.
在本研究中,我们报道了聚乙烯吡咯烷酮(PVP)是一种合适的有机溶剂,用于通过厨房搅拌机技术将水溶液中的结晶石墨机械剥离成石墨烯。利用扫描电镜、拉曼散射和紫外可见光谱对石墨烯样品的形貌、结构和光学性质进行了表征。扫描电镜显示厚度约4 nm的石墨烯薄片的折叠形态。通过对石墨/PVP分散体的剥离处理,得到了具有低缺陷的高质量石墨烯。拉曼光谱上~1582 cm−1的G波段与碳原子的伸缩振动有关。没有观察到G带的展宽,这表明石墨烯结构中没有基面缺陷,这可能是在厨房搅拌机剥离过程中引入的。2D带强度与G带强度之比为1.66 (I2D/IG>1), 2D带半最大全宽值为79.88 cm-1,表明其为少层石墨烯结构。通过D和G波段强度比识别的缺陷数量ID/IG为0.18,显著低于基面缺陷的氧化石墨烯(> 1)和超声分散石墨烯(~ 0.6)。用紫外可见光谱对石墨烯分散体进行了表征,在270 nm附近观察到的最小透过率归因于石墨烯中芳香族C-C键的π→π*跃迁。在270 ~ 800 nm之间观察到的光学透过率最小值和整体高透过率下降值强烈表明在色散中存在二维材料,从而证实了石墨通过混合成功地剥离为石墨烯。我们演示了一种简单无毒的方法,使用厨房搅拌器和环保的聚乙烯吡咯烷酮作为有机去角质剂来生产高质量的FLG片材,没有缺陷。
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引用次数: 0
Method of “cleaning” the surface of responsive elements of silicon p-i-n photodiodes from dislocations “清洗”硅p-i-n光电二极管响应元件表面位错的方法
Pub Date : 2023-06-30 DOI: 10.15407/hftp14.02.182
M. Kukurudziak
Investigating the formation of inversion layers (IL) at the Si-SiO2 interface in the manufacturing technology of silicon photodetectors, some dynamics of dislocations after isothermal annealing were revealed, which were absent in samples without inversion. After selective etching of samples with inversion layers, localization of dislocations on the periphery of responsive elements (RE) with accumulation of guard rings (GR) or other elements of n+-type topology outside the RE was observed. This testified to the movement of dislocations on the surface of the Si-SiO2 structures with IL in the direction of the periphery of the crystal during isothermal annealing, which contributed to a significant decrease in the density of structural defects in RE. The described phenomenon can be used to obtain highly doped defect-free silicon structures. Since the presence of dislocations or other violations of the crystal lattice negatively affect the parameters of the products. In the case of using the described phenomenon as a technological method of “cleaning” the surface of silicon structures, there is a need for controlled formation of IL. One of the methods of forming inversion layers can be thermal oxidation in hydrochloric acid vapors according to the principle of dry-wet-dry oxidation (for p-type silicon). Another method that does not require additional materials is the annealing of Si-SiO2 structures at a temperature of 900–950 Celsium degrees in a nitrogen atmosphere for ≥ 240 minutes. Inversion channels, in this case, will be formed due to the redistribution and diffusion of metal impurities in the oxide (which were introduced during previous thermal operations) to the Si-SiO2 interface. In the described case, these structural defects after annealing were localized in the GR, which is also an active element of the phododiodes, as it limits the dark current of the RE, accordingly, the dark current of the GR should also be low. To be able to implement this method, it is necessary to create passive n+-regions on the periphery of the crystals, limited by oxide, which will be the locations of defects after annealing. It can be both separate areas of arbitrary shape and a concentric ring outside the GR. Elements that will be the locations of defects on the periphery can be cut off at the stage of separating the substrates into crystals. After annealing, it is necessary to remove the IL and form an anti-reflective coating by any known method, since the presence of inversion channels contributes to the growth of dark currents. When examining the morphology of defect localization areas after annealing under high-magnification microscopes and with the help of an atomic force microscope, the formation of hexagonal and round defects, which are partial marginal Frank dislocation loops, was observed. The mechanism of dislocation movement described in this article has not been thoroughly studied by us and requires additional research, but it may be related to Cottrel
研究了硅光电探测器制造工艺中Si-SiO2界面反转层(IL)的形成,揭示了等温退火后的位错动力学,而非反转样品则不存在这些动力学。用反转层对样品进行选择性蚀刻后,可以观察到响应元件(RE)外围有保护环(GR)积累或响应元件外n+型拓扑元素的位错局部化。这证明在等温退火过程中,含有IL的Si-SiO2结构表面的位错沿晶体外围方向移动,这有助于RE中结构缺陷密度的显著降低。所描述的现象可以用于获得高掺杂的无缺陷硅结构。由于位错或其他违反晶格的存在对产品的参数产生负面影响。在使用所描述的现象作为“清洁”硅结构表面的技术方法的情况下,需要控制IL的形成。根据干-湿-干氧化原理(对于p型硅),形成反转层的方法之一可以是在盐酸蒸气中进行热氧化。另一种不需要额外材料的方法是将Si-SiO2结构在900-950摄氏度的温度下在氮气气氛中退火≥240分钟。在这种情况下,由于氧化物中的金属杂质(在之前的热操作中引入的)重新分布和扩散到Si-SiO2界面,将形成反转通道。在本例中,这些退火后的结构缺陷被定位在GR中,GR也是光电二极管的一个有源元件,它限制了RE的暗电流,因此GR的暗电流也应该是低的。为了能够实现这种方法,有必要在晶体的外围创建受氧化物限制的被动n+区域,这将是退火后缺陷的位置。它既可以是任意形状的单独区域,也可以是GR外的同心圆。在将衬底分离成晶体的阶段,可以切断外围将成为缺陷位置的元素。退火后,有必要通过任何已知的方法去除IL并形成抗反射涂层,因为反转通道的存在有助于暗电流的生长。在高倍显微镜和原子力显微镜下观察退火后缺陷局部化区的形貌,观察到六角形和圆形缺陷的形成,这些缺陷是部分边缘Frank位错环。本文中描述的位错运动机理尚未被我们深入研究,需要进一步的研究,但它可能与Cottrell气氛及其与IL的相互作用有关
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引用次数: 0
Anodic aluminum oxide-membrane prepared in electrolyte “oxalic acid – matter with carbon nanodots” 在“草酸-碳纳米点物质”电解液中制备阳极氧化铝膜
Pub Date : 2023-06-30 DOI: 10.15407/hftp14.02.237
K. Kudelko, L. Rozhdestvenska, L. Ponomarova, V. M. Оgenko
Anodic porous alumina has been studied and used as nanoscale structure, coating, template in different applications. The porous anodic alumina oxide could be described as numerous hexagonal cells and looks like cellular structure. In this work we report about results of study anodizing of aluminum with usage of electrolyte: “oxalic acid electrolyte-matter with carbon nanodots”. It was received anodic aluminum oxide-membrane with aluminum supporting; calcination was used as post treatment. The aluminum substrate allows one to fix the membrane in the cells. Methods: processes of anodizing was provided in 0.3M oxalic acid with addition of colloid system of carbon nanodots, temperature of process was controlled at range of 10 degree Celsius, aluminum foil (anode) and platinum plate (cathode) were used; thickness of aluminum foil was 0.1 µm; morphology and structure of anodic aluminum oxide-membrane were determined with usage of electron scanning microscope; the contact angle between the surface of anodic aluminum oxide-membrane and deionized water was measured with “drop” methodology. Calcium content was monitored with a conductometer. The content of proteins was determined with photometry (micro Lowry’s method). It was found that contact angle of the surface of anodic aluminum oxide-membrane obtained in electrolyte “oxalic acid-matter with carbon nanodots” and deionized water is 38 degrees. Adding colloidal system of carbon nanodots to the acid electrolyte acts as a hydrophilizer, changes the size of the porous surface: as a result, it is possible to control the porosity of the films. Calcination of anodic aluminum oxide-membrane at 500 degree Celsius lead to expansion and thinning of pore walls. Anodic aluminum oxide-membrane was tested for dialysis process for milk whey separation. The membrane obtained in electrolyte: “oxalic acid-matter with carbon nanodots” showed a greater degree of rejection of protein particles in comparison with a similar membrane obtained in electrolyte of oxalic acid. The advantage of using carbon nanodots in acid electrolyte is the simplicity and environmental friendliness of the synthesis. The approach, which involves the addition of a colloidal system with carbon nanomaterial, allows one to avoid using a strongly acidic electrolyte for obtaining membranes with smaller pores. One of the ways for using of anodic oxide aluminum-membrane is the dialysis of biological fluids, for example, milk whey.
阳极多孔氧化铝在纳米结构、涂层、模板等方面得到了广泛的应用。多孔阳极氧化氧化铝可以被描述为许多六边形的细胞,看起来像细胞结构。本文报道了用“草酸电解质-碳纳米点物质”电解铝的研究结果。采用铝支撑阳极氧化铝膜;后处理采用煅烧法。铝基板允许人们将膜固定在细胞中。方法:在0.3M草酸中加入碳纳米点胶体体系进行阳极氧化,工艺温度控制在10℃范围内,采用铝箔(阳极)和铂板(阴极);铝箔厚度为0.1µm;用电子扫描显微镜观察了阳极氧化铝膜的形貌和结构;用“滴法”测量了阳极氧化铝膜表面与去离子水的接触角。用电导仪监测钙含量。用光度法(显微洛瑞法)测定蛋白质含量。结果表明,在“草酸-碳纳米点物质”电解液中制备的阳极氧化铝膜表面与去离子水的接触角为38度。在酸性电解液中加入碳纳米点胶体体系,起到亲水剂的作用,改变了多孔表面的大小,从而可以控制薄膜的孔隙率。在500摄氏度下煅烧阳极氧化铝膜会导致孔壁膨胀和变薄。对阳极氧化铝膜透析分离乳清进行了试验研究。与在草酸电解质中获得的类似膜相比,在“草酸-碳纳米点物质”电解质中获得的膜对蛋白质颗粒的排斥程度更高。在酸性电解液中使用碳纳米点具有合成简单、环境友好的优点。这种方法,包括添加碳纳米材料的胶体系统,允许人们避免使用强酸性电解质来获得具有较小孔隙的膜。阳极氧化铝膜的一种应用方法是对乳清等生物液体进行透析。
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引用次数: 0
Embedded atoms in a crystalline hexagonal structure 晶体六边形结构中的嵌入原子
Pub Date : 2023-06-30 DOI: 10.15407/hftp14.02.210
Z. Matysina, A. Zolotarenko, O. Zolotarenko, T. Myronenko, D. V. Schur, E. Rudakova, M. Chymbai, A. Zolotarenko, I. Zagorulko, O. Havryliuk
As part of the work, the hexagonal structure of B19 type metals as hydrogen sorbents will be considered. That is, crystal lattices are considered, where atoms of impurities (hydrogen) are introduced into the interstices of the metal. To do this, we present an image of the B19 structure itself. In this work, the solubility of hydrogen in the crystal structure of B19 type metals was studied using the configuration method, and the dependence on the composition of the alloy and temperature was found in the substitution of nodes and interstices. Also, in the work the degrees of long-range order at the nodes are considered and the parameters of the correlation in the substitution are determined. A graphical view of the effect of atomic order on the solubility of impurities is given. The calculated data obtained in the work coincide with the experimental data of other studies, and the obtained calculation formulas make it possible to determine the energy parameters of the alloys, which is a certain scientific value of the work. The proposed system takes into account only atomic interaction and absorption (dissolution) and diffusion of interstitial atoms into the bulk of the crystal structure; therefore, it is possible to predict the introduction of only a hydrogen atom. Thus, the results obtained in the work of the correlation parameters for the distribution of atoms only in octapores or only in tetrapores allow a deeper study of the physical characteristics of alloys of the B19 type and an understanding of the processes of hydrogen sorption by the working bodies of hydrogen storage.
作为工作的一部分,将考虑 B19 型金属的六边形结构作为氢吸附剂。也就是说,在考虑晶格时,要将杂质(氢)原子引入金属间隙。为此,我们将展示 B19 结构本身的图像。在这项工作中,我们使用构型法研究了氢在 B19 型金属晶体结构中的溶解度,并发现了节点和间隙的置换与合金成分和温度的关系。此外,该研究还考虑了节点处的长程有序度,并确定了置换中的相关参数。给出了原子序对杂质溶解度影响的图表。工作中获得的计算数据与其他研究的实验数据相吻合,获得的计算公式使得确定合金的能量参数成为可能,这是该工作的一定科学价值所在。所提出的系统只考虑了原子的相互作用和吸收(溶解)以及间隙原子向晶体结构主体的扩散;因此,可以预测只引入一个氢原子的情况。因此,工作中获得的仅在八孔隙或仅在四孔隙中原子分布的相关参数结果,可以更深入地研究 B19 型合金的物理特性,并了解储氢工作体的吸氢过程。
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Himia, Fizika ta Tehnologia Poverhni
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