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1.
《Ceramics International》2022,48(9):12699-12711
The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li2O–K2O–Na2O–CaO–MgO–ZrO2–Al2O3–P2O5–SiO2 glass system has been reported here. Increased amount of MgO enhanced the participation of Al2O3 as a glass network former along with [SiO4] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (~10 GPa) and elastic modulus (~127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.  相似文献   

2.
《Ceramics International》2023,49(5):7737-7745
Glass-ceramics without nucleating agents usually undergo surface crystallization, which deteriorates the overall performance of the products. In this paper, we evaluated the effects of the metastable MgAl2Si3O10 crystalline phase on the crystallization behavior of a MgO–Al2O3–SiO2 (MAS) glass without nucleating agents and mechanical properties of the glass-ceramics obtained. The results demonstrated that the precipitation of metastable MgAl2Si3O10 crystallites promotes the crystallization mechanism transformed from surface crystallization into volume crystallization with two-dimensional crystal growth. Furthermore, the grain size of MgAl2Si3O10 near the surface of the prepared glass-ceramics was larger than that of MgAl2Si3O10 inside, which helps to generate compressive stress and improves its mechanical properties. The glass-ceramics containing metastable MgAl2Si3O10 phase exhibited an enhanced hardness in the range of 7.6 GPa–9.5 GPa for indentation loads ranging from 2.94 N to 98 N, and indentation size effect behavior was observed in Vickers hardness tests of both MAS glass and glass-ceramics. The load-independent hardness values for MAS glass and glass-ceramics were reliably evaluated by the modified proportional specimen resistance (MPSR) model of 7.1 GPa and 7.6 GPa, respectively, with a high correlation coefficient of more than 0.9999. This work reveals the unexploited potential of the metastable phase in improving the crystallization ability and mechanical properties of glass-ceramics.  相似文献   

3.
Laser joining of ZrO2 ceramics using glasses and glass ceramics as sealing components requires optimized systems. The ternary systems SiO2–BaO–B2O3 and BaO–SrO–SiO2 were selected as a basis for development of suitable glass compositions for the laser joining process. Additives such as CaO, TiO2, Al2O3, and MgO were used to control the crystallization processes and hence the thermal expansion coefficients during glass synthesis. The glass viscosity, the strength of the ceramic-glass-ceramic joint, and the joint tightness are other important glass properties which were optimized for the laser process. For glass G018-345, this yielded strengths of up to 225 MPa (Weibull modulus of m = 8.6) and He leak rates of up to 4.3 × 10−5 mbar l s−1. Because of the varying viscosities obtained, the optimized glass systems could be used selectively in a temperature range of 700–900 °C.  相似文献   

4.
To obtain an alkali-free glass substrate with enhanced properties for thin-film transistor–liquid crystal displays (TFT–LCDs) applications, we chose a base glass composed of 3B2O3-15Al2O3-58SiO2-22MgO-0.5SrO-1.5MgF2 (mol%) for nucleation–crystallization. The results show that when the nucleation–crystallization processes of the base glass are 810 °C/6 h + 880 °C/6–9 h, the prepared GC/6–GC/9 glass-ceramics exhibit enhanced properties because of the precipitation of nano-sized cordierite. The transmittances in the visible range of the GC/6–GC/9 glass-ceramics exceed 85%, the densities are 2.564–2.567 g/cm3, thermal expansion coefficients are 2.934–3.059 × 10-6/°C (25–300 °C), compressive strengths are 417–589 MPa, bending strengths are 141–259 MPa, Vickers hardnesses are 6.8–7.8 GPa, and strain points are approximately 735 °C. Considering these properties, the prepared GC/6–GC/9 glass-ceramics have good potential as candidate materials for alkali-free glass substrates. Additionally, these results demonstrate that it is feasible to improve the properties of alkali-free glass substrates by nucleation–crystallization.  相似文献   

5.
《Ceramics International》2021,47(18):25997-26009
The effects of adding ZrO2 and TiO2 at the expense of MgF2 on the crystallization, microstructure, mechanical properties, thermal properties and electrical properties of mica glass-ceramics based on the SiO2–MgO–MgF2–K2O system were investigated by the differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), microhardness tester and resistivity tester. The electrical properties were discussed emphatically. The results showed that the additions of ZrO2 and/or TiO2 at the expense of MgF2 effectively increase the viscosity, the glass transition temperatures (Tg) and the crystallization temperatures (Tp) of the glasses. The crystallization activation energy (Ec) of the amorphous glasses varied with the nucleating agents was discussed in depth. It was discovered that the nucleating agents had no effect on the crystal phase type but had a certain effect on the crystallinity and microstructure. Tetrasilicic fluoromica and enstatite were precipitated at different crystallization temperatures. Due to the non-stoichiometric ratio of tetrasilicic fluoromica crystal, the prepared glass-ceramics had high dielectric constant (24.4–34.3) and volume resistivity (>2 × 1011 Ω cm) at 25 °C, and the dielectric loss was almost zero.  相似文献   

6.
The physicochemical features of the phase formation upon crystallization of monolithic glasses of the strontium diborate stoichiometric composition are investigated. It is demonstrated that the first phase crystallizing on the surface of the SrO · 2B2O3 glass is the strontium borate Sr4B14O25, which plays the role of a precursor for the subsequent crystallization of the SrB4O7 borate. The temperature corresponding to the maximum crystal nucleation rate on the surface and the time of complete “operation” of nuclei are determined using differential thermal analysis. The optical glass-ceramics prepared by the two-stage crystallization are surface-crystallized glasses in which the filling density of the surface is approximately equal to 30% and the content of the main phase SrB4O7 is as high as ∼ 70%. No second harmonic generation of neodymium laser radiation in the glass-ceramics is observed because of both the absence of the preferred orientation of SrB4O7 nonlinear optical crystals and the small crystal sizes (considerably smaller than the coherence length of the SrB4O7 crystal) in the direction perpendicular to the glass surface.  相似文献   

7.
《Ceramics International》2016,42(5):5842-5857
The effect of SrO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Sr: (54−x)CaO–xSrO–6P2O5–40SiO2 and S2Sr: (16−x)CaO–xSrO–4P2O5–80SiO2 (x=0, 1, 3 and 5) stabilized at 700 °C on their structure (XRD, FTIR) and bioactive properties (SBF test) was investigated. Preliminary in vitro tests using human articular chondrocytes of selected A2Sr glass were also conducted. Moreover, the subject of this study was to detect the changes on material properties after heat treatment at 1300 °C. The results show that the effect of strontium substitution on structure, bioactivity and crystallization after treatment at both the above temperatures strongly depends on CaO/SiO2 molar ratio. The presence of 3–5 mol% of strontium ions creates more expanded glass structure but does not markedly affect crystallization ability after low temperature treatment. Sintering at 1300 °C of A2 type glasses results in crystallization of pseudowollastonite, hydroxyapatite and also Sr-substituted hydroxyapatite for 3–5 mol% of SrO substitution. The increase of strontium concentration in silica-rich materials after sintering leads to appearance of calcium strontium phosphate instead of calcium phosphate. Bioactivity evaluation indicates that substitution of Sr for Ca delays calcium phosphate formation on the materials surface only in the case of silica-rich glasses treated at 700 °C. Calcium-rich glasses, after both temperature treatments, reveals high bioactivity, while crystal size of hydroxyapatite decreases with increasing Sr content. High temperature treatment of high-silica glasses inhibits their bioactivity. Preliminary in vitro tests shows Sr addition to have a positive effects on human articular chondrocytes proliferation and to inhibit cell matrix biomineralization.  相似文献   

8.
《Ceramics International》2022,48(14):20053-20061
The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li2O–MgO–Al2O3–SiO2 glass-ceramic for the application of joining Si3N4 ceramics. We investigated the influence of the MgO/Al2O3 composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi2O6 and Mg2SiO4 were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg2SiO4. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10?6/°C, which was very close to that of Si3N4 ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si3N4 ceramic surface was 32° and the interface was well bonded.  相似文献   

9.
《Ceramics International》2023,49(16):26860-26870
The degradation of environmentally friendly CaO–Al2O3–SiO2–B2O3 (CASB) glass-ceramics, which consist of anorthite and glass phase, was investigated in three natural organic acid solutions. The results indicated that citric acid had the most significant effect on the degradation of CASB glass-ceramics. While the chemical stability of anorthite is relatively poor, the glass phase also contributed significantly to the effective degradation of CASB glass-ceramics. Subsequently, Ba2+ or Sr2+ was used for full or partial substitution of Ca2+ in CASB glass-ceramics, and the degradation-controlling mechanism of the substituted CASB glass-ceramics was further researched. The full substitution of Ca2+ in CASB glass-ceramics by the two cations resulted in the occurrence of borate [BO4] units in the glass phases, and the interlinkage of [BO4] with broken silicate [SiO4] network structures caused a complementary network effect. Consequently, the degradation of CASB glass-ceramics by organic acids was reduced due to the improvements in the chemical stability of the modified glass-ceramics. Additionally, degradation control can also be achieved based on a mixed-alkali effect, originating from the partial substitution of Ca2+ in CASB glass-ceramics by Ba2+ or Sr2+. The degradable glass-ceramics have the potential to be applied in low-temperature co-fired ceramic technology because of their good physical properties, which include a dielectric constant of 3–5, a dielectric loss as low as 10−3, a coefficient of thermal expansion of 3–9 × 10−6/°C, and an average bending strength of about 47 MPa. Noticeably, the development of the degradable glass-ceramics is helpful to the low-cost and pollution-free recycling of valuable metal electrodes, which is significant for the sustainable development of electronic packaging technologies.  相似文献   

10.
《Ceramics International》2023,49(1):216-225
In order to obtain lithium disilicate glass-ceramics for dental restoration with both high strength and high translucency, lithium disilicate glass-ceramics with different MgO contents were prepared by melt-casting and heat treatment method. The effects of MgO content on the crystallization temperature, microstructure and flexural strength of lithium disilicate glass-ceramics were investigated. The results indicate that Mg2+ exists in the form of [MgO4] in the network of lithium disilicate glass-ceramics when the MgO content is 0.56 mol% (M0.56), which is beneficial to increasing the homogeneity and thermal stability of the glass system, and short rod-like lithium disilicate crystals can be formed after heat treatment at 840°C. Thus, the obtained lithium disilicate glass-ceramics exhibit excellent comprehensive performance, with the flexural strength being 312 ± 23 MPa, and the average transmittance of visible light being 37.3% (d = 1.62 mm). Especially, the glass-ceramic sample shows better translucency than the commercially available products. The research results are of great significance for developing high performance lithium disilicate glass ceramics and promoting its broad application in the field of dental restoration.  相似文献   

11.
《Ceramics International》2023,49(13):21443-21448
Glass-ceramics show a great application potential in sustainable development, environmental protection, high temperature, high voltage resistance, and so on. Given the breakdown strength has a great contribution to the energy storage density, alkali-free niobate-based glass-ceramics have emerged as a prominent energy storage material. In this study, the 13.64BaCO3-13.64SrCO3-32.72Nb2O5-40SiO2 alkali-free glass-ceramics were optimized in thickness and crystallization temperature. The thinning of thickness improves the breakdown strength. At the same time, the dielectric constant gets a maximum value by adjusting the crystallization temperature. Therefore, an ultra-high theoretical energy storage density of 27.47 J·cm−3 is obtained. In addition, the finite element software simulates the electric field distribution and electric potential evolution during the development of electric branches, which illustrates the role of glass phase in hindering the development of electric branches and partaking the high electric field. Finally, the effective energy storage density obtained by using P-E loops is 1.49 J·cm−3 under 850 kV/cm.  相似文献   

12.
《Ceramics International》2023,49(16):26934-26942
The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO2-Al2O3-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO2 ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm3), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.  相似文献   

13.
《Ceramics International》2020,46(9):13724-13731
Lithium di-silicate (LS2) glass-ceramics modified with copper oxide using the formula: 34.83Li2O–xCuO–(65.17-x)SiO2 (where; x = 1, 2, 4 and 6 mol%) were prepared by melt-quenching followed by controlling heat-treatment. 6 mol% of MnO or Fe2O3 transition metal oxides was added instead of SiO2 in the high CuO-content composition. The effect of the transition cations on phase formation, microstructure, density, thermal expansion, and electrical conductivity was investigated as a function of the controlled crystallization. Results show that up to 4 mol%, Cu+2 was hosted in stable Li2Si2O5 structure. This enhanced the crystal formation, including Li2Si2O5 and its solid solution (ss), Li2SiO3, Li2Cu5(Si2O7)2, CuMn6SiO12, LiFeSi2O6 (ss), and the orthosilicate Li2FeSiO4 (ss). The prepared materials had different density values ranged from 2.35 to 2.79 g/cm3 for glass and varied from 2.43 to 3.15 g/cm3 for glass–ceramics, whereas the α-values of glass-ceramics ranged in the 95–165 × 10−7/°C. The progress of electrical properties in glass-ceramics, as a function of composition, was studied. It was markedly improved by adding different transition cations especially, Fe+3. The study reveals that the incorporation of transition metal ions in LS2 composition has a positive effect on the physical-chemical properties of the prepared glass-ceramics. Therefore, it constitutes to prepare future glass-ceramic applications as hermetic seals of metals as well solid electrolyte materials.  相似文献   

14.
《Ceramics International》2023,49(3):4872-4880
CaO–B2O3–SiO2–Ta2O5 (CBST) glass-ceramics, with different Ta2O5 content, (up to 6 mol%), have been prepared by using glass melt quenching followed by heat treatment between 800 and 880 °C. The Fourier Transform Infrared (FTIR) results showed that the stronger the attraction of Ta5+ to the oxygens in the BO33? and SiO32? structures, the more easily the B–O and Si–O bonds will be destroyed. The underlying reason is most probably the high field strength of Ta5+, which results in a weakening of the vibration intensities of the [BO3] and [SiO4] units. Moreover, the Differential Scanning Calorimetry (DSC) results showed that the softening point (Tg), crystallization starting temperature (Tc1), and exothermic crystallization peak temperature (Tp1), of the CaSiO3 phase, shifted to higher values with the addition of Ta2O5. Also, the crystallization activation energy (Ea) and the glass stability factor (ΔT) of the CaSiO3 phase increased, which indicated that the CaSiO3 phase of the glass became inhibited by the addition of Ta2O5. It was, thus, obvious that there was a need of glass characterization. The results of the crystallization kinetics showed that the critical cooling rate decreased with the addition of Ta2O5, which indicated that the viscosity of the system had increased. The CBST glass-ceramics, containing 1 mol% Ta2O5, that were sintered at 875 °C for 15 min showed excellent dielectric properties: εr = 6.22 and tanδ = 1.19 × 10?3 (1 MHz). To sum up, CaO–B2O3–SiO2–Ta2O5 glass-ceramics are potential low temperature co-fired ceramic substrate materials.  相似文献   

15.
Nanocrystalline yttria-stabilized tetragonal zirconia polycrystal (nc-Y-TZP) powders coated with silicate based glasses were cold isostatically pressed and sintered near to the full density (98–99%). Two glasses with different compositions were used: 93 SiO2–1 Na2O–6 SrO (mol%) (designated as SNS glass) and 58 SiO2–29 Al2O3–13 SrO (designated as SAS glass). Uniaxial compression tests of the pure (glass-free) nc-Y-TZP samples yielded strain rates as high as 2·10−4 s−1 under 60 MPa at 1300 °C. Comparable strain rates were measured in the SNS glass-containing samples, with the maximum of 3·10−4 s−1 at 1300 °C under a stress of 80 MPa (5 vol.% SNS glass content). Compression tests under 100 MPa exhibited relatively high strain rates of 5·10−4 and 10−4 at 1300 °C and 1200 °C, respectively, in the 15 vol.% SAS glass samples. The strain rates measured in the SAS glass-containing samples were achieved at temperatures lower by 100 °C compared to the similar strain rates in the glass-free and SNS glass-containing samples. The microstructure of the deformed samples was similar to that of samples before deformation, within which the ultrafine and equiaxed character of the grains was preserved. Clear evidence for cooperative grain boundary sliding was observed in the SAS glass-containing samples.  相似文献   

16.
Sm3+-doped SrO–Al2O3–SiO2 glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated. The results indicate that the crystal phase in this system is monocelsian (SrAl2Si2O8). Under the excitation with blue light (475 nm) the Sm3+-doped SrO–Al2O3–SiO2 glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm, which can be assigned to the 4G5/26HJ/2 (J = 5, 7, 9, 11) electron transitions in Sm3+ ions, respectively. With the increase of nucleation/crystallization temperature, the crystallite part rises from 66 to 79%. Besides, by increasing crystallization temperature or concentration of Sm3+, the samples emission located at 565, 605 and 650 nm is intensified significantly. We envision that, by fine controlling and combining of these three (green, orange and red) lights in an appropriate proportion, the Sm3+-doped glass-ceramics are promising luminescence materials for white light-emitting diodes devices.  相似文献   

17.
Glass beads of the Sr2MgSi2O7 stoichiometric composition and a non-stoichiometric composition with higher SiO2/SrO ratio doped with Eu2O3/Dy2O3 were prepared through aerodynamic levitation coupled to CO2 laser heating. The glass beads were subsequently treated at 1100 ºC to produce glass-ceramics with Sr2MgSi2O7: Eu2+, Dy3+ as the main crystalline phase. The doped glasses exhibit red emissions; after crystallisation, the corresponding glass-ceramics emit blue light under UV excitation. The starting glass composition considerably affects the crystallisation process, resulting in Sr2MgSi2O7 glass-ceramics with very different microstructures which, in turn, have a significant influence on the luminescence properties. The photoluminescence emission spectra of the glass-ceramics under UV light show a broadband emission (λ = 400–500 nm) with a main peak assigned to the typical Eu2+ transition under excitation at 365 nm. Both the intensity of the emission and the persistence time significatively increase on decreasing temperature. Glass-ceramics from the non-stoichimetric glass composition co-doped with 1Eu2O3/0.5Dy2O3 (mol%.) provided the longest persistence times.  相似文献   

18.
《Ceramics International》2023,49(7):10652-10662
Transparent glass-ceramics containing eucryptite and nepheline crystalline phases were prepared from alkali (Li, Na) aluminosilicate glasses with various mole substitutions of Al2O3 for SiO2. The relationships between glass network structure and crystallization behavior of Li2O–Na2O–Al2O3–SiO2 (LNAS) glasses were investigated. It was found that the crystallization of the eucryptite and nepheline in LNAS glasses significantly depended on the concentration of Al2O3. LNAS glasses with the addition of Al2O3 from 16 to 18 mol% exhibited increasing Q4 (mAl) structural units confirmed by NMR and Raman spectroscopy, which promoted the formation of eucryptite and nepheline crystalline phases. With the Al2O3 content increasing to 19–20 mol%, the formation of highly disordered (Li, Na)3PO4 phase which can serve as nucleation sites was inhibited and the crystallization mechanism of glass became surface crystallization. Glass-ceramics containing 18 mol% Al2O3 showed high transparency ~84% at 550 nm. Moreover, the microhardness, elastic modulus and fracture toughness are 8.56 GPa, 95.7 GPa and 0.78 MPa m1/2 respectively. The transparent glass-ceramics with good mechanical properties show high potential in the applications of protective cover of displays.  相似文献   

19.
Crystallization, microstructure and mechanical behavior of strontium fluorphlogopite glass-ceramics, SrO·4MgO·Al2O3·6SiO2·2MgF2, was studied by varying the fluorine content. A number of glass-ceramics of each glass batch with excess MgF2 [SR0 (0% MgF2), SR5 (5% MgF2) and SR10 (10% MgF2)] were prepared by heating at its respective nucleation temperature followed by at different crystallization temperatures (780–1150 °C). Differential Thermal Analysis (DTA), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Micro Hardness Indenter were used to study the crystallization, microstructure and mechanical behavior of resulting three glass batches. DTA analysis revealed that the peak crystallization (Tp) and glass transition (Tg) temperatures decreased with increasing fluorine content that also lowers down the activation energy (E) as evident from crystallization kinetics. Hardness and fracture toughness values are higher for less fluorine containing glass-ceramics when they are treated isothermally. However, more fluorine based glass-ceramics is found to be more machinable than the less fluorine one.  相似文献   

20.
《Ceramics International》2021,47(18):25467-25474
The crystallization behaviour and thermo-magnetic characteristics of glass-ceramic based on the 15Li2O–20ZnO–10CaO–55SiO2 system doped with varied Fe2O3 additions (0.0125, 0.025, and 0.05 mol) are described in this work. In some cases, Al2O3 was also added to the iron-containing sample. Glasses were successfully prepared by melt-quenching technique and converted into glass-ceramics by controlled heat-treatment, using DTA, SEM, XRD, and VSM techniques. The density, thermal expansion coefficients (TCE), and magnetic characteristics of the glass-ceramic were examined. XRD results confirmed characteristic peaks for various phases like quartz, Li2ZnSiO4, wollastonite, Li2Si2O5, ZnFe2O4, and β-spodumene. By doping Fe2O3 and Al2O3 with lowering annealing temperature, the particle size was reduce, resulting in glass-ceramics with a more uniform and dense microstructure. The density of glass-ceramics rises from 2.74 g/cm3 to 3.45 g/cm3, whereas the TCE values in average 14–78 × 10−7/°C with temperature range of 25–500 °C. The doped glass-ceramics have superior magnetic properties with saturation magnetization (0.143–0.548 emu/g), the coercivity force (65.116–86.359 G), and remanence magnetization (0.074–0.436 emu/g). Under an alternating magnetic field, the presence of the Zn-ferrite phase in the glass-ceramics improves their magnetic properties and increases their heat-generating capability. Certain features of the doped glass-ceramics control the extensive variety of possibilities for their usage in various magnetic applications particularly for cancer hyperthermia treatment.  相似文献   

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