252 resultados para Sinterização.


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Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq

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The present study aims to evaluate the potential use of bagasse ash from sugar cane (CBC) as a flux, replacing phyllite and/or feldspar in standard industrial mass production of enameled porcelain, verifying the possibility of the CBC contribute to the overall reduction of the coefficient of thermal expansion of the ceramic mass. To this end, as a result of the research, we characterized the raw material components of the standard mass (clay, phyllite, kaolin, feldspar, quartz and talc) and the residue of BCC, by testing by XRF, XRD, AG, DTA and ATG. Specimens (CDP) were manufactured in the dimensions of 100 mm x 50 mm x 8 mm in uniaxial matrix under compaction pressure of 33 MPa, assembled in batches of 3 units subsequently sintered at temperatures of 1150°C to 1210°C by varying the Rating Scale at 10°C, heating and cooling ramp of 50°C/min and 25°C/min, with levels of 1 min, 3 min, 5 min, 8 min, 10 min, 15 min, 30 min and 60 min. analyzing the results of the physical properties of water absorption (WA), linear firing shrinkage (LFS), dilatometric analysis (DTA), flexural strain (SFT) and SEM of the sintered bodies in order to verify the adequacy of CDP to ISO 13006, ISO 10545, NBR 13816 standards; NBR 13817 and NBR 13818. The study showed that the formulations that best suit the requirements of the standards are:. G4 - which was applied in 10% of replacing the CBC phyllite, sintering temperature 1210 ° C for 10 min and porch, and F3 - with application of 7.5% of CBC to replace the feldspar in the sintering temperatures of 1190°C, 1200°C and 1210°C for 10 min and porch. These formulations showed better performance regarding the formation of primary and secondary mullite, with considerable reduction of cracks and pores, meeting the prerequisites of standards for glazed porcelain. The results shows that the use of the CBC as a flux in the preparation of porcelain mass meets standard parameters for the manufacture of the product, and thereby can reduce environmental impact and the cost of production. Therefore, it is recommended to use this residue in the ceramics industry, due to its industrial, commercial and collaborative viability for sustainability.

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In States of Paraíba (PB) and Rio Grande do Norte (RN), northeast of Brazil, the most significant deposits of non-metallic industrial minerals are pegmatites, quartzites and granites, which are located in Seridó region. Extraction of clay, quartz, micas and feldspars occurs mainly in the cities of Várzea (PB), OuroBranco (RN) and Parelhas (RN). Mining companies working in the extraction and processing of quartzite generate large volumes of waste containing about 90% SiO2 in their chemical composition coming from quartz that is one of the basic constituents of ceramic mass for the production of ceramic coating. Therefore, this work evaluates the utilization of these wastes on fabrication of high-quality ceramic products, such as porcelain stoneware, in industrial scale. Characterization of raw materials was based on XRF, XRD, GA, TGA and DSC analysis, on samples composed by 57% of feldspar, 37% of argil and 6% of quartzite residues, with 5 different colors (white, gold, pink, green and black). Samples were synthesized in three temperatures, 1150°C, 1200°C and 1250°C, with one hour isotherm and warming-up tax of 10°C/min. After synthesizing, the specimens were submit to physical characterization tests of water absorption, linear shrinkage, apparently porosity, density, flexural strain at three points. The addition of 6% of quartzite residue to ceramic mass provided a final product with technological properties attending technical norms for the production of porcelain stoneware; best results were observed at a temperature of 1200°C. According to the results there was a high iron oxide on black quartzite, being their use in porcelain stoneware discarded by ethic and structural question, because the material fused at 1250°C. All quartzite formulations had low water absorption when synthesized at 1200°C, getting 0.1% to 0.36% without having gone through the atomization process. Besides, flexural strain tests overcame 27 MPa reaching the acceptance limits of the European Directive EN 100, at 1200°C synthesizing. Thus, the use of quartzite residues in ceramic masses poses as great potential for the production of porcelain stoneware.

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This work presents a new ceramic material obtained through the incorporation of solid waste from the steel industry and known as dedusting powder PAE - in ceramic formulations based on clay, potassium and sodium feldspars, kaolin and talc. Formulations were prepared with ceramic residue levels of 0% (basic mass - MB), 2%, 4% and 8%, subjected to firing at temperatures of 1000 ° C, 1050ºC, 1100ºC and 1150ºC for periods of 15 min. and 120 min. The physicchemical and mechanical properties of these ceramic formulations were determined based on the firing temperature, residence time in the oven and the percentage of waste. Since the physicochemical and mechanical properties of the sintered materials were evaluated by chemical analysis techniques (fluorescence X-rays - FRX), particle size distribution, specific surface area, apparent density, structural analysis by diffraction of X-rays (DRX) and characterization of surface by scanning electron microscopy (SEM). The magnetic response characteristics and the pattern of magnetic ferrites of the samples were analyzed in the assay conditions, having noticed that the saturation magnetic susceptibility depend on the sintering temperature of the material and it is associated with its crystal structure. From the analysis results, it was concluded that the ceramic material with better physical and mechanical properties is obtained when the 8% from PAE residue is added to standard formulation under the burn time of 15 minutes and temperature of 1150ºC.

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This work shows that the synthesis by combustion is a prominent alternative to obtain ceramic powders of higher oxides, nanostructured and of high purity, as the ferrites of formulas Co(1-x)Zn(x)Fe2O4 e Ni(1-x)Zn(x)Fe2O4 with x ranging from 0.2 mols, in a range from 0.2 ≤ x ≥ 1.0 mol, that presents magnetic properties in coexistence of ferroelectric and ferrimagnetic states, which can be used in antennas of micro tapes and selective surfaces of low frequency in a range of miniaturized microwaves, without performance loss. The obtainment occurred through the combustion process, followed by appropriate physical processes and ordered to the utilization of the substrate sinterization process, it gave us a ceramic material, of high purity degree in a nanometric scale. The Vibrating Sample Magnetometer (VSM) analysis showed that those ferritic materials presents parameters, as materials hysteresis, that have own behavior of magnetic materials of good quality, in which the magnetization states can be suddenly changed with a relatively small variation of the field intensity, having large applications on the electronics field. The X-ray Diffraction (XRD) analysis of the ceramic powders synthesized at 900 °C, characterize its structural and geometrical properties, the crystallite size and the interplanar spacing. Other analysis were developed, as Scanning Electron Microscopy (SEM), X-ray Fluorescence (XRF), electric permittivity and the tangent loss, in high frequencies, through the equipment ZVB - 14 Vector Network Analyzer 10 MHz-14 GHz, of ROHDE & SCHWART.

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The ceramics industry generates waste at various stages of that process, defective products, waste from burning solid fuels, among others. This waste is dumped in landfills, garbage dumps or directly on roads, which has a negative environmental impact. This paper presents a study to incorporate the waste of algaroba wood and chamote (scrap pieces of ceramic already sintered), in to the ceramic material for making sealing blocks. The methodological procedures consist in the characterization of chemical and mineralogical residues, raw materials, and physical-mechanical of the formulations of mixes with clay, silt and waste. By pressing test pieces were produced using a pressure of 200 kgf/cm², varying compositions in the range of 0%, 5%, 10% and 15% by weight of residue. The sintering was performed in a muffle furnace, with the temperature levels of 850 ° C, 900 ° C, 950 ° C, 1000 ° C and 1050 ° C. The evaluated physical and mechanical properties were: Water Absorption, Linear Shrinkage Burning, Apparent Porosity, Apparent Density and Mechanical Resistance to Flexion. Analysis was carried out by Scanning Electron Microscopy on fracture surfaces of the specimens. Evaluation of linear shrinkage property drying and firing , water absorption and mechanical resistance to compression of the sealing blocks 5% wood ash residue, sintered at 900 °C hold temperature in the laboratory the products manufactured on an industrial scale. The main results, it was found on the viability of using the residues of algaroba wood and to confer refractory properties of the ceramic product. The main results, it was concluded feasibility of using the ash residues algaroba wood to impart refractory properties to the ceramic product and the residue of chamote, being derived from the own ceramic product not interfere with the properties, when used in a percentage of up to 5%.Since the residue of chamote being derived from the ceramic product itself had no effect on the properties. Studies in the laboratory have shown that the incorporation of up to 5% of these residues may be adopted as an alternative technology to reduce the environmental impact caused by the industrial sector, without compromising the final properties of the material, since the results on an industrial scale showed absorption values 11.66 and 11.74 of water and waste products respectively, within the parameters of NBR - 15,270, since the mechanical strength was 1.25 MPa and 0.94 MPa respectively for products with and without residue, lower than the minimum required by the technical standard that is 1.5 MPa.

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The ceramics industry generates waste at various stages of that process, defective products, waste from burning solid fuels, among others. This waste is dumped in landfills, garbage dumps or directly on roads, which has a negative environmental impact. This paper presents a study to incorporate the waste of algaroba wood and chamote (scrap pieces of ceramic already sintered), in to the ceramic material for making sealing blocks. The methodological procedures consist in the characterization of chemical and mineralogical residues, raw materials, and physical-mechanical of the formulations of mixes with clay, silt and waste. By pressing test pieces were produced using a pressure of 200 kgf/cm², varying compositions in the range of 0%, 5%, 10% and 15% by weight of residue. The sintering was performed in a muffle furnace, with the temperature levels of 850 ° C, 900 ° C, 950 ° C, 1000 ° C and 1050 ° C. The evaluated physical and mechanical properties were: Water Absorption, Linear Shrinkage Burning, Apparent Porosity, Apparent Density and Mechanical Resistance to Flexion. Analysis was carried out by Scanning Electron Microscopy on fracture surfaces of the specimens. Evaluation of linear shrinkage property drying and firing , water absorption and mechanical resistance to compression of the sealing blocks 5% wood ash residue, sintered at 900 °C hold temperature in the laboratory the products manufactured on an industrial scale. The main results, it was found on the viability of using the residues of algaroba wood and to confer refractory properties of the ceramic product. The main results, it was concluded feasibility of using the ash residues algaroba wood to impart refractory properties to the ceramic product and the residue of chamote, being derived from the own ceramic product not interfere with the properties, when used in a percentage of up to 5%.Since the residue of chamote being derived from the ceramic product itself had no effect on the properties. Studies in the laboratory have shown that the incorporation of up to 5% of these residues may be adopted as an alternative technology to reduce the environmental impact caused by the industrial sector, without compromising the final properties of the material, since the results on an industrial scale showed absorption values 11.66 and 11.74 of water and waste products respectively, within the parameters of NBR - 15,270, since the mechanical strength was 1.25 MPa and 0.94 MPa respectively for products with and without residue, lower than the minimum required by the technical standard that is 1.5 MPa.

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Ceramic materials the alumina base are large industrial applications. They are required for these products, specific characteristics obtained by following strict criteria during the manufacturing process. However, after life, not always these products are reused by a suitable waste management process. In ceramist context, advance research aimed at the reuse of waste aimed at obtaining ceramics and composite materials, with marked reduction of conventional raw materials. Aiming to generate scientific, technological and environmental contribution, this work studied to obtain a composite of alumina ceramic (Al2O3) and sodium beta alumina (NaAl11O17 ), and as starting materials the residue of the ceramic insulator of spark plugs, as a source alumina (Al2O3) powder and unusable sodium bicarbonate (NaHCO3) of fire extinguishers, as a source of sodium oxide (Na2O). The final ceramic product was obtained from a conventional mixture of sodium aluminum oxide in appropriate molar proportions. Sample spark plugs were obtained, discarded by lifetime, specific to a manufacturer, which, after passing through mechanical stress (grinding, magnetic purification, washing, drying and grinding the high energy), which resulted in residue powder with ceramic content of 84.34 % alumina (Al2O3), found by FRX chemical analysis, the phases present and identified by DRX. The dry chemical fire extinguisher, baking soda-based (NaHCO3) with expired, was obtained through direct collection of the waste generated during maintenance. Subjected to heat treatment at 120 °C , the NaHCO3 powder was decomposed in sodium oxide ( Na2O), which, subjected to chemical analysis (FRX) and mineralogical (DRX) revealed a content of 86.62 % sodium oxide (Na2O) . In the following steps the experimental procedure, chemical formulations were made on a molar basis of the starting material (1:9, 1:10 and 1:11 de Na2O/ Al2O3) inclusion of additives, milling parameters, sieve analysis, dilatometry, conformation of specimens, sintering in firing steps at 800 °C , 1000 °C and 1.200 °C with varying stays 30 , 60 and 120 minutes in each of the levels. The characterization of the final product was made by the following physical tests: water absorption, porosity, linear shrinkage, mineralogical analysis by DRX and microstructural analysis by MEV. A higher formation of sodium beta alumina (NaAl11O17), in sintered specimens in levels of 1.200 °C and 120 minutes, despite the prevailing coexistence of alpha phase alumina (Al2O3). From the results obtained opens up prospects for the reuse of waste studied in this work, the potter context and in other technological areas.

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Ceramic materials the alumina base are large industrial applications. They are required for these products, specific characteristics obtained by following strict criteria during the manufacturing process. However, after life, not always these products are reused by a suitable waste management process. In ceramist context, advance research aimed at the reuse of waste aimed at obtaining ceramics and composite materials, with marked reduction of conventional raw materials. Aiming to generate scientific, technological and environmental contribution, this work studied to obtain a composite of alumina ceramic (Al2O3) and sodium beta alumina (NaAl11O17 ), and as starting materials the residue of the ceramic insulator of spark plugs, as a source alumina (Al2O3) powder and unusable sodium bicarbonate (NaHCO3) of fire extinguishers, as a source of sodium oxide (Na2O). The final ceramic product was obtained from a conventional mixture of sodium aluminum oxide in appropriate molar proportions. Sample spark plugs were obtained, discarded by lifetime, specific to a manufacturer, which, after passing through mechanical stress (grinding, magnetic purification, washing, drying and grinding the high energy), which resulted in residue powder with ceramic content of 84.34 % alumina (Al2O3), found by FRX chemical analysis, the phases present and identified by DRX. The dry chemical fire extinguisher, baking soda-based (NaHCO3) with expired, was obtained through direct collection of the waste generated during maintenance. Subjected to heat treatment at 120 °C , the NaHCO3 powder was decomposed in sodium oxide ( Na2O), which, subjected to chemical analysis (FRX) and mineralogical (DRX) revealed a content of 86.62 % sodium oxide (Na2O) . In the following steps the experimental procedure, chemical formulations were made on a molar basis of the starting material (1:9, 1:10 and 1:11 de Na2O/ Al2O3) inclusion of additives, milling parameters, sieve analysis, dilatometry, conformation of specimens, sintering in firing steps at 800 °C , 1000 °C and 1.200 °C with varying stays 30 , 60 and 120 minutes in each of the levels. The characterization of the final product was made by the following physical tests: water absorption, porosity, linear shrinkage, mineralogical analysis by DRX and microstructural analysis by MEV. A higher formation of sodium beta alumina (NaAl11O17), in sintered specimens in levels of 1.200 °C and 120 minutes, despite the prevailing coexistence of alpha phase alumina (Al2O3). From the results obtained opens up prospects for the reuse of waste studied in this work, the potter context and in other technological areas.

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O carbeto de boro tem efeito inibidor sobre a densificação da matriz de alumina. A maior densidade obtida foi de 80% da densidade teórica. A sinterização foi conduzida nas temperaturas de 1700, 1750 e 1800°C/1 hora em atmosfera de argônio. A caracterização microestrutural foi realizada por difração de raios X, MEV e MET. Foi observada a formação de uma fase identificada por MET como sendo A13B06.

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Os sensores lambda resistivos possuem as vantagens de simplicidade e menor custo relativamente à utilização generalizada de sensores potenciométricos de oxigénio. Nesse sentido, os titanatos de estrôncio têm sido alvo de diversos estudos. Para a produção de uma relação inequívoca entre a condutividade destes materiais e a pressão parcial de oxigénio é necessária a adição de um dopante dador que suprime a condução eletrónica do tipo-p na região de pressões parciais de oxigénio próximas de ar. Contudo, a adição de um dopante dador produz respostas lentas destes materiais quando densos a variações da pressão parcial de oxigénio. Além da preparação usual dos pós por reação do estado sólido, foram preparadas diversas composições por mecanossíntese. Tal relaciona-se com o fato exaustivamente reportado de as amostras destes materiais, especialmente quando dopados com dadores, apresentarem comportamentos dependentes das condições de processamento. Teve ainda o intuito de avaliar a viabilidade da sua preparação por este método, e consequentemente verificar se este método de preparação, que presumivelmente produzirá pós com composição mais homogénea e mais reativos, permite alterar/manipular a resposta obtida por amostras com eles produzidas. Foram preparados diversos filmes, tipologia muito usada na produção de sensores resistivos, e amostras porosas com diversas composições à base de titanato de estrôncio produzidos com variadas condições de processamento. Foram realizadas diversas caracterizações sobre estes espécimes numa tentativa de melhor compreender as propriedades destes materiais e a dependência destas com parâmetros microestruturais como o tamanho de grão e a porosidade. Foi verificado que os exemplares de titanato de estrôncio não dopado, quer em filmes quer em amostras porosas, apresentam um comportamento elétrico semelhante ao apresentado por amostras densas deste material. Apurou-se ainda, que as suas características apresentam uma variação ténue com a alteração das condições de processamento. Já espécimes de titanato de estrôncio dopados com dador revelam uma forte dependência das suas propriedades com as condições de processamento utilizadas, nomeadamente, a temperatura de sinterização e o tempo de permanência a essa temperatura. Para o fabrico de sensores resistivos de oxigénio poderá ser preferível o recurso a amostras porosas pelo facto de mais facilmente se manipularem as suas características microestruturais e devido à exclusão dos problemas associados à interação entre o substrato de alumina e o filme. As composições não dopadas são as indicadas para esta função se a gama de pressões de oxigénio a avaliar for relativamente pouco extensa sendo aconselhadas as composições dopadas com dador se for pretendida uma medição da pressão parcial de oxigénio em zonas mais extensas correspondentes à queima com deficiência ou excesso de oxigénio. Mesmo em amostras de elevada porosidade poderá ocorrer resposta transiente do material dopado com dador.

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O presente trabalho incidiu sobre uma família de eletrólitos sólidos cerâmicos à base de óxido de zircónio, incluindo ainda óxido de magnésio como dopante, normalmente designados de Mg-PSZ (zircónia parcialmente estabilizada com magnésia). Dependendo da composição e condições de processamento (perfil de sinterização) estes materiais podem exibir interessantes combinações de propriedades mecânicas, térmicas e elétricas que permitem a sua utilização no fabrico de sensores de oxigénio para metais fundidos. O uso de sensores é hoje essencial numa lógica de controlo de processo e eficiência energética. No sentido de tentar compreender como influenciar estas propriedades, exploraram-se diversos níveis de dopante (de 2,5 até 10 mol%, com acréscimos de 2,5 mol% de MgO), diversas velocidades de arrefecimento (2, 3 e 5 °C.min-1) a partir de uma condição igual de patamar de sinterização (1700 °C, 3 horas), e ainda alguns ciclos de sinterização mais complexos, com patamares intermédios inseridos no processo de arrefecimento, com o objetivo de tentar alterar os processos de nucleação e crescimento de fases. Na realidade, as transformações de fases a que este tipo de materiais se encontra sujeito (cúbica  tetragonal  monoclínica, para temperaturas decrescentes), possuem diferentes velocidades características (uma é difusiva a outra displaciva), permitindo este tipo de condicionamento. Os materiais obtidos foram alvo de caracterização estrutural e microestrutural, complementada por um conjunto de outras técnicas de caracterização física como a espectroscopia de impedância, dilatometria e dureza. Os resultados obtidos confirmam a complexidade das relações entre processamento e comportamento mas permitiram identificar condições de potencial interesse prático para as aplicações em vista.

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O principal objetivo deste trabalho é preparar um cermeto do tipo Al2O3/Ti(C,N) com propriedades mecânicas adequadas à sua utilização na maquinação de materiais do tipo DIN ISO 513:K01-K10 e ISO H01-H10. De forma a incrementar a sinterabilidade do cermeto investigou-se o efeito da adição de dopantes metálicos, nomeadamente alumínio metálico (Al) e hidreto de titânio (TiH2) e o efeito da substituição da moagem convencional por moagem de alta energia. As variáveis das etapas principais de processamento, i.e., da moagem, prensagem e sinterização, foram selecionadas com trabalho realizado quer na Universidade de Aveiro quer na empresa Palbit. Foram preparadas três composições do cermeto Al2O3/Ti(C,N) com adições de 5%TiH2, 1%Al e 5%TiH21%Al através da moagem de alta energia. Os parâmetros de moagem, i.e. a velocidade de rotação, o rácio bolas/pó e o tempo de moagem foram otimizados para os seguintes valores: 350 rpm, 10:1 e 5 h, respetivamente. A utilização da moagem de alta energia permitiu uma redução do tamanho de partícula dos pós até aproximadamente 100 nm e a obtenção de uma boa uniformidade da distribuição das fases (Al2O3+Ti(C,N)). A etapa de conformação foi efetuada por prensagem uniaxial seguida de prensagem isostática. A avaliação da reatividade dos cermetos através de dilatometria em atmosfera de vácuo revelou que a densificação é maioritariamente realizada em estado sólido. A adição de apenas 1%Al é a menos efetiva para a densificação. Os cermetos foram sinterizados através de sinterização convencional em forno de vazio a 1650ºC e prensagem a quente (1650ºC com uma pressão uniaxial de 25 MPa). Os valores de densificação obtidos, aproximadamente 80% e 100%, respetivamente, indicam que a aplicação de pressão durante a sinterização é efetiva para atingir densificações elevadas nos compactos, compatíveis com as suas aplicações tecnológicas. As propriedades mecânicas de dureza e de tenacidade avaliadas nos três cermetos apresentaram valores aproximados de 1800-1900 HV50 para a dureza e entre 5.4 e 7.7 MPa.m1/2 para a tenacidade à fratura.

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The main objective of this work is the development of a hardmetal components (WC-6%Co) recovery method by thermal deposition process. The thermal deposition technique used was HVOF (high velocity oxygen-fuel). The HVOF enables depositions of thick coatings (100-500 µm) with low porosity levels, high hardness and excellent adhesion. Before deposition, hardmetal samples with different geometries (plates and cylinders) were finished in order to have different roughness. The influence of these parameters in adhesion was studied. After this step, different re-sintering temperatures were used, in order to determine which one allows to obtain the maxima densification, elements distribution and metallurgical bonding. The re-sintering promotes the densification of the coating, with an increase of its hardness and metallurgical bonding formation. The inclusion of an intermetallic layer was tested along with different layer parameters. In liquid phase sintering (1383 and 1455 ºC) a complete densification of the coating occurred, while a bonding between the substrate and the coating only partially happened. The results of SEM/EDS show low levels of porosity and a complete and uniform distribution of the elements of the alloy. The cylindrical samples without intermetallic layer showed the lowest level of porosity and best metallurgical bonding. When the substrate surface was polished (Ra = 0.05 mm) lower levels of porosity and greater metallurgical bonding were found for both geometries. Taking into account the results obtained in this study, we can conclude that the implementation of this process is appropriate for cylindrical components with a polished surface. In these components the intermetallic layer is unnecessary and punctual defects like pores can be repaired with this process.

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The synthesis and optimization of two Li-ion solid electrolytes were studied in this work. Different combinations of precursors were used to prepare La0.5Li0.5TiO3 via mechanosynthesis. Despite the ability to form a perovskite phase by the mechanochemical reaction it was not possible to obtain a pure La0.5Li0.5TiO3 phase by this process. Of all the seven combinations of precursors and conditions tested, the one where La2O3, Li2CO3 and TiO2 were milled for 480min (LaOLiCO-480) showed the best results, with trace impurity phases still being observed. The main impurity phase was that of La2O3 after mechanosynthesis (22.84%) and Li2TiO3 after calcination (4.20%). Two different sol-gel methods were used to substitute boron on the Zr-site of Li1+xZr2-xBx(PO4)3 or the P-site of Li1+6xZr2(P1-xBxO4)3, with the doping being achieved on the Zr-site using a method adapted from Alamo et al (1989). The results show that the Zr-site is the preferential mechanism for B doping of LiZr2(PO4)3 and not the P-site. Rietveld refinement of the unit-cell parameters was performed and it was verified by consideration of Vegard’s law that it is possible to obtain phase purity up to x = 0.05. This corresponds with the phases present in the XRD data, that showed the additional presence of the low temperature (monoclinic) phase for the powder sintered at 1200ºC for 12h of compositions with x ≥ 0.075. The compositions inside the solid solution undergo the phase transition from triclinic (PDF#01-074-2562) to rhombohedral (PDF#01-070-6734) when heating from 25 to 100ºC, as reported in the literature for the base composition. Despite several efforts, it was not possible to obtain dense pellets and with physical integrity after sintering, requiring further work in order to obtain dense pellets for the electrochemical characterisation of Li Zr2(PO4)3 and Li1.05Zr1.95B0.05(PO4)3.