Toward the identification of social signatures in ceramic production - An archaeological case study.

Ceramic analysis has been concerned with categorizing types according to vessel shape and size for describing a given material culture at a particular time. This analysis' long tradition has enabled archaeologists to define cultural units across time. However, going into the analysis of sub-typological variations is rarely done, although their meanings bear significant consequences on the understanding of ties between individuals and social units. This study, aiming to assess whether it is possible to identify social signatures, focuses on a single archaeological ceramic type. For this propose, we selected a corpus of 235 storage jars from two distinct periods: storage jars from the Intermediate Bronze Age (the 25th -20th century BCE); and the Oval Storage Jar type (hereafter: OSJ) from the Iron Age II (the late 9th-early 6th century BCE). The vessels selected were 3-D scanned to extract accurate geometric parameters and analyzed through an advanced shape analysis. The study results show that integrating computational and objective analysis methods, focusing on the "minute variation" within a single ceramic type, yields substantial insights regarding the relationship between variability and social units. In addition to the methodological guidelines and the suggested "work protocol" for further studies, the results shed light on the social organization of the Intermediate Bronze Age and the Iron Age II in Southern Levant.

Análise microestrutural e propriedades mecânicas de cerâmicas vítreas cristalizadas por energia de micro-ondas / Microstructural characterization and mechanical properties of glassceramics crystallized by microwave energy

O objetivo deste trabalho foi verificar a viabilidade de um processo alternativo de cristalização por meio de energia de micro-ondas, e estabelecer um protocolo de cristalização para três vitrocerâmicas comerciais; além de avaliar o efeito deste processo na microestrutura e propriedades mecânicas das mesmas. A hipótese nula foi que a cristalização por meio de energia de micro-ondas não afetou as características microestruturais e consequentemente as propriedades destes materiais cerâmicos. Foram confeccionados 180 discos a partir de blocos de três diferentes vitrocerâmicas: dissilicato de lítio (IPS e.max CAD, Ivoclar Vivadent) e silicatos de lítio reforçados por zircônia (I ­ Suprinity, Vita Zahnfabrik; II ­ Celtra, Dentsply), seguindo as dimensões da norma ISO 6872 (12 x 1,2 mm). Foram testadas três temperaturas de cristalização em forno de micro-ondas (700ºC, 770ºC e 850ºC), e os testes de flexão biaxial, MEV e DRX foram utilizados para definir qual a temperatura em que as cerâmicas apresentaram melhor comportamento. Os testes de densidade, translucidez, rugosidade superficial, dureza Vickers e desgaste de três e dois corpos foram realizados com as amostras cristalizadas apenas nas temperaturas selecionadas para cada cerâmica. Para o grupo DL-mo, a temperatura de cristalização foi 850ºC, e a resistência do material aumentou (422,4 ± 63,53). Para os grupos SLZ1-mo e SLZ2-mo, a temperatura de cristalização foi 770ºC, com resistências aproximadamente semelhantes ao grupo convencional (302,8 ± 37,86 e 268,7 ± 44,85 respectivamente). Os testes de translucidez e densidade mostraram uma relação estatística em que as cerâmicas com maior densidade possuem maior translucidez, como as SLZ1-mo e SLZ2-mo. O teste de rugosidade não apresentou diferença estatística para os parâmetros Ra e Rsm, apenas para Rz. Para o teste de desgaste de três corpos, o grupo cristalizado em micro-ondas sofreu menor taxa de desgaste (0.22 ± 0.71) do que o grupo convencional (0.62 ± 0.4); enquanto para o teste de desgaste de dois corpos a forma de cristalização não foi uma variável estatisticamente significante. SLZ1 apresentou maior taxa de desgaste, independentemente da forma de cristalização (1.30 ± 1.79). Concluiu-se que o processo de cristalização é viável para vitrocerâmicas, e que diferentes temperaturas de cristalização resultam em diferentes microestruturas e propriedades mecânicas. A temperatura de cristalização para DL, utilizando energia de micro-ondas, é 850ºC e para SLZ1 e SLZ2 é 770ºC. Cerâmicas cristalizadas em forno de micro-ondas apresentam menor taxa de desgaste, maior resistência à flexão, maiores módulos de Weibull, e consequentemente maior longevidade(au)

The aim of this study was to verify the viability of an alternative process of crystallization using microwave energy and to establish a crystallization protocol for three commercial glass-ceramics; besides evaluating the effect of this process on the microstructure and mechanical properties of them. The null hypothesis was that the crystallization by microwave energy did not affect the microstructural characteristics and consequently the mechanical properties of these ceramic materials. 180 discs were made from blocks of three different glass-ceramics: lithium disilicate (IPS e.max CAD, Ivoclar Vivadent) and lithium silicates reinforced by zirconia (I - Suprinity, Vita Zahnfabrik; II - Celtra, Dentsply); according to ISO 6872 (dimensions: 12 x 1.2 mm). Three crystallization temperatures were tested in a microwave oven (700ºC, 770ºC and 850ºC), and the biaxial flexure, SEM and XRD tests were performed to define the temperature in which the ceramics presented their best behavior. Density, translucency, surface roughness, Vickers hardness and three and two-body wear tests were performed with the crystallized samples only at the selected temperatures for each ceramic. For DL-mo group, the crystallization temperature was 850ºC and material's resistance increased (422.4 ± 63.53). For SLZ1-mo and SLZ2-mo groups, the crystallization temperature was 770ºC, with resistances approximately similar to the conventional group (302.8 ± 37.86 and 268.7 ± 44.85 respectively). Translucency and density tests showed that the higher the density, the higher the translucency. The roughness test showed no statistical difference for Ra and Rsm parameters, only for Rz. For the three-body wear test, the microwave crystallized group suffered lower wear rate (0.22 ± 0.71) than the conventional group (0.62 ± 0.4); while for the two-body wear test the crystallization approach was not a statistically significant variable. SLZ1 presented higher wear rates, regardless of the crystallization approach (1.30 ± 1.79). It was concluded that the crystallization process is viable for glass ceramics, and that different crystallization temperatures result in different microstructures and mechanical properties. The crystallization temperature for DL using microwave energy is 850ºC and for SLZ1 and SLZ2 is 770ºC. Microwave oven crystallized ceramics have a lower wear rate, higher flexural resistance, higher Weibull modulus, and consequently higher longevity(AU)

In vitro bioactivity studies of ceramic structures isolated from marine sponges.

In this work, we focused on the potential of bioceramics from different marine sponges-namely Petrosia ficiformis, Agelas oroides and Chondrosia reniformis-for novel biomedical/industrial applications. The bioceramics from these sponges were obtained after calcination at 750 °C for 6 h in a furnace. The morphological characteristics were evaluated by scanning electron microscopy (SEM). The in vitro bioactivity of the bioceramics was evaluated in simulated body fluid (SBF) after 14 and 21 d. Observation of the bioceramics by SEM after immersion in SBF solution, coupled with spectroscopic elemental analysis (EDS), showed that the surface morphology was consistent with a calcium-phosphate (Ca/P) coating, similar to hydroxyapatite crystals (HA). Evaluation of the characteristic peaks of Ca/P crystals by Fourier transform infrared spectroscopy and x-ray diffraction further confirmed the existence of HA. Cytotoxicity studies were carried out with the different ceramics and these were compared with a commercially available Bioglass(®). In vitro tests demonstrated that marine bioceramics from these sponges are non-cytotoxic and have the potential to be used as substitutes for synthetic Bioglass(®).

A novel method for isolation and recovery of ceramic nanoparticles and metal wear debris from serum lubricants at ultra-low wear rates.

UNLABELLED: Ceramics have been used to deliver significant improvements in the wear properties of orthopaedic bearing materials, which has made it challenging to isolate wear debris from simulator lubricants. Ceramics such as silicon nitride, as well as ceramic-like surface coatings on metal substrates have been explored as potential alternatives to conventional implant materials. Current isolation methods were designed for isolating conventional metal, UHMWPE and ceramic wear debris. In this paper, we describe a methodology for isolation and recovery of ceramic or ceramic-like coating particles and metal wear particles from serum lubricants under ultra-low and low wear performance. Enzymatic digestion was used to digest the serum proteins and sodium polytungstate was used as a novel density gradient medium to isolate particles from proteins and other contaminants by ultracentrifugation. This method demonstrated over 80% recovery of particles and did not alter the size or morphology of ceramic and metal particles during the isolation process. STATEMENT OF SIGNIFICANCE: Improvements in resistance to wear and mechanical damage of the articulating surfaces have a large influence on longevity and reliability of joint replacement devices. Modern ceramics have demonstrated ultra-low wear rates for hard-on-hard total hip replacements. Generation of very low concentrations of wear debris in simulator lubricants has made it challenging to isolate the particles for characterisation and further analysis. We have introduced a novel method to isolate ceramic and metal particles from serum-based lubricants using enzymatic digestion and novel sodium polytungstate gradients. This is the first study to demonstrate the recovery of ceramic and metal particles from serum lubricants at lowest detectable in vitro wear rates reported in literature.

Loop-mediated isothermal amplification (LAMP) assays for rapid detection and differentiation of Nosema apis and N. ceranae in honeybees.

Nosemosis is a contagious disease of honeybees (Apis mellifera) manifested by increased winter mortality, poor spring build-up and even the total extinction of infected bee colonies. In this paper, loop-mediated isothermal amplifications (LAMP) were used for the first time to identify and differentiate N. apis and N. ceranae, the causative agents of nosemosis. LAMP assays were performed at a constant temperature of 60 °C using two sets of six species-specific primers, recognising eight distinct fragments of 16S rDNA gene and GspSSD polymerase with strand displacement activity. The optimal time for LAMP and its Nosema species sensitivity and specificity were assessed. LAMP only required 30 min for robust identification of the amplicons. Ten-fold serial dilutions of total DNA isolated from bees infected with microsporidia were used to determine the detection limit of N. apis and N. ceranae DNAs by LAMP and standard PCR assays. LAMP appeared to be 10(3) -fold more sensitive than a standard PCR in detecting N. apis and N. ceranae. LAMP methods developed by us are highly Nosema species specific and allow to identify and differentiate N. apis and N. ceranae.

Fossils as candidate material for orthopedic applications.

Ceramic powders from fossil deposits were thoroughly characterized from the material point of view and sintered to produce massive components. The raw material, a mixture of apatite minerals, feldspars, and quartz, seems ideally suitable to obtain a biologically compatible glass ceramic. Preliminary in vitro tests of proliferation and adhesion of MG63 human osteoblast-like cell line on a selected sample are encouraging. Results are correlated with sintering conditions and phase composition: the fossil can be sintered to almost full density at temperatures as low as 900 °C and seems to quickly promote cell activation with respect to hydroxylapatite.

Biomorphous porous hydroxyapatite-ceramics from rattan (Calamus Rotang).

The three-dimensional, highly oriented pore channel anatomy of native rattan (Calamus rotang) was used as a template to fabricate biomorphous hydroxyapatite (Ca(5)(PO(4))(3)OH) ceramics designed for bone regeneration scaffolds. A low viscous hydroxyapatite-sol was prepared from triethyl phosphite and calcium nitrate tetrahydrate and repeatedly vacuum infiltrated into the native template. The template was subsequently pyrolysed at 800 degrees C to form a biocarbon replica of the native tissue. Heat treatment at 1,300 degrees C in air atmosphere caused oxidation of the carbon skeleton and sintering of the hydroxyapatite. SEM analysis confirmed detailed replication of rattan anatomy. Porosity of the samples measured by mercury porosimetry showed a multimodal pore size distribution in the range of 300 nm to 300 microm. Phase composition was determined by XRD and FT-IR revealing hydroxyapatite as the dominant phase with minimum fractions of CaO and Ca(3)(PO(4))(2). The biomorphous scaffolds with a total porosity of 70-80% obtained a compressive strength of 3-5 MPa in axial direction and 1-2 MPa in radial direction of the pore channel orientation. Bending strength was determined in a coaxial double ring test resulting in a maximum bending strength of approximately 2 MPa.

Fabrication of bioactive glass-ceramic foams mimicking human bone portions for regenerative medicine.

A technique for the preparation of bioglass foams for bone tissue engineering is presented. The process is based on the in situ foaming of a bioglass-loaded polyurethane foam as the intermediate step for obtaining a bioglass porous monolith, starting from sol-gel synthesized bioglass powders. The obtained foams were characterized using X-ray diffraction analysis, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy observations. The material was assessed by soaking samples in simulated body fluid and observing apatite layer formation. Diagnostic imaging taken from human patients was used to reconstruct a human bone portion, which was used to mould a tailored scaffold fabricated using the in situ foaming technique. The results confirmed that the obtained bioactive materials prepared with three-dimensional processing are promising for applications in reconstructive surgery tailored to each single patient.

Preparation of porous hydroxyapatite with interconnected pore architecture.

Since pore connectivity has significant effects on the biological behaviors of biomedical porous hydroxyapatite (PHA), the preparation of PHA with interconnected pore architecture is of great practical significance. In the present study, PHA with highly interconnected architecture was prepared via a simple burnout route with rod-like urea as the porogen. Microscopy and porosimetry data showed that the as-prepared PHA had open and interconnected pore structure with the average fenestration size of about 120 microm. Open pores occupied up to 98% of the total porosity. The compressive strength and modulus of the as-prepared PHA were respectively 1.3-7.6 MPa and 4.0-10.4 GPa.

Development of graded hydroxyapatite/CaCO(3) composite structures for bone ingrowth.

Ceramic composites composed of constituents with different bone cell reactions present an interesting consideration for a new bone replacement material. The first component of the composite used in this study, hydroxyapatite, is known to be replaced by natural tissue significantly slower than the second, calcium carbonate, which has limited structural stability. A graded hydroxyapatite/calcium carbonate composite with bimodal component distribution was developed using a combined slip infiltration and dip-coating technique from a porous polyurethane sponge replica. A graded hydroxyapatite scaffold with porosities from 5 to 90% was produced and then infiltrated with a calcium carbonate slip and sintered. The resultant composite had improved mechanical properties compared with the monolith as measured by crushing and moduli tests.

Biodegradation and bioabsorption innovation of the functionally graded bovine bone-originated apatite with blood permeability.

Bioabsorbable and functionally graded apatite (fg-HAp) ceramics were designed using bovine bone by the calcination and partial dissolution-precipitation methods. The fg-HAp ceramics that were developed had gradual distributions of the degree of crystallinity and the grain size of single-phase hydroxyapatite from the surface layer of the pore wall to the bulk structure region. Calcination at 1073 K gave a specific surface area of 30 m2 x g-1 and porosities of 60-80%. The pore structure of the fg-HAp was classified into two regions: a macro-pore region (100-600 microm) originating from spongy bone and a micro-pore region (10-160 nm) related to body fluid permeation and blood permeability. By implantation in subcutaneous tissue of rat, it was confirmed that body fluid permeated the bulk region of the fg-HAp ceramics through the micro-pores. The volumetric populations occupied by body fluid were 60% at 4 weeks and 68% at 8 weeks in the ceramics explants, indicating drastic bioabsorption, although the body fluid was found to be immunopositive for an albumin as the main serum protein in blood. On the fg-HAp ceramics developed here, the bioabsorption rate could be controlled by careful selection of the calcination temperature. These ceramics can be applied as new biomimetic ceramics exhibiting surface and bulk degradations and cellular absorption by giant cells.

Hard tissue remodeling using biofabricated coralline biomaterials.

Biotechnical and biomedical approaches were combined in an attempt to identify potential uses of biofabricated marine carbonate materials in biomedical applications, particularly as biomatrices for remodeling bone and cartilage tissue. After grafting, it is desirable for bone ingrowth to proceed as quickly as possible because the strength of the implanted region depends on a good mechanical bond forming between the implant and surrounding regions in the body. Ingrowth can take place as a result of growth of tissue and cells into the implanted porous material, or it may be promoted by transplanting cells seeded onto such a material. The rate at which ingrowth occurs is dependent on many factors, including pore size and the interconnectivity of the implanted structure. In vivo graftings into osteochondral defects demonstrated that our biofabricated porous material is highly biocompatible with cartilage and bone tissue. The biofabricated matrix was well incorporated into the biphasic osteochondral area. Resorption was followed by bone and cartilage formation, and after 4 months, the biomaterial had been replaced by new tissue. Ossification was induced and enhanced without introduction of additional factors. We believe that this is the first time that such biofabricated materials have been used for biomedical purposes. In face of the obvious environmental disadvantages of harvesting from limited natural resources, we propose the use of bioengineered coralline and other materials such as those cultured by our group under field and laboratory conditions as a possible biomatrix for hard tissue remodeling.

Bone induction by porous glass ceramic made from Bioglass (45S5).

Porous glass ceramic, which was prepared from Bioglass powder (45S5, U.S. Biomaterials) by foaming with diluted H(2)O(2) solution and sintering at 1000 degrees C for 2 h, was implanted as cylinders (5 mm in diameter and 6 mm in length) in thigh muscles of dogs for 3 months. Histological observation was made on thin un-decalcified sections. Bone formation was histologically found in pores of all implants (X16) retrieved from 16 dogs. The bone tissue was also identified with backscattered scanning electron microscopy observation (BSE) and energy dispersive X-ray microanalysis (EDX). This is the first report of bone induction in soft tissues of animals by glass ceramic that has long been recognized as a bioactive (osteoconductive) biomaterial. The present results justify the impetus to investigate the osteoinductivity of calcium phosphate-based biomaterials, to study the mechanism of bone induction (osteoinduction) by calcium phosphate-based biomaterials, to develop osteoinductive calcium phosphate-based biomaterials, and to examine the relation between osteoinduction and osteoconduction.

Possibilities for strengthening hydroxyapatite ceramics.

Some physics during heating and sintering of powder pressings of hydroxyapatite (HA) under conventional (usual) conditions have been studied. It is revealed that heating and firing of the pressings of a middle-dispersity powder are accompanied by release of gases. The gas release hinders and can stop the shrinkage (sintering). The microhardness is low and has a complicated distribution on the surface and in the volume of ceramics. A slight degassing (drying) of the pressing before sintering heightens the density and improves the microhardness characteristics of the ceramics. The shrinkage stop effect is eliminated in pressings of a fine powder. On the basis of the results, a technique and some methods for quality improvement of ceramics were proposed and approbated. They consisted of the manufacture of samples of a mixture of two powders with different dispersity, use of a press technique with two male dies, thermal treatment of pressing before sintering, and the choice of moderate sintering conditions. The resulting ceramics had a density close to the theoretical, almost homogeneous microhardness distribution in the sample and much higher values of microhardness and compressive strength.

Preparation of a biphasic porous bioceramic by heating bovine cancellous bone with Na4P2O7.10H2O addition.

Sintered bovine cancellous bone exhibited excellent biocompatiblity, high porosity and have an interconnecting porous structure allowing for bone ingrowth. However, the main mineral constitution of sintered bovine bone-hydroxyapatite (Ca10(PO4)6(OH)2, HAP) seems to be too stable in vivo. For improving its bioactivity, the calcined bovine bone removing the organic substance by burning process-with different quantities of sodium pyrophosphate (Na4P2O7.10H2O, NP) addition was heated to a high temperature to transform its crystalline phase constitution from HAP into TCP/HAP biphasic or other multiphasic structures. Results revealed that the calcined bovine bone without NP addition, exhibited a pure form of HAP characterized pattern during heating. Its thermal behavior was similar to stoichiometric HAP, it gradually lost its OH- ions and transformed into oxyhydroxyapatite at high temperature. After being doped into calcined bovine bone, NP would react with HAP to form betaBTCP and NaCaPO4 around 600 degrees C. At 900 degrees C, doped NP would completely react with HAP and the NaCaPO4 would further react with HAP to form more betaBTCP in the system. With NP increasing in the calcined bovine bone, HAP would gradually convert into different crystalline phase compositions of TCP/HAP, TCP/HAP/NaCaPO4 or TCP/NaCaPO4 at high temperature. By heating calcined bovine cancellouse bone with different quantities of NP we could obtain different crystalline phase compositions of natural porous bioceramic in this study.

Pulmonary retention of ceramic fibers in silicon carbide (SiC) workers.

The fibrous inorganic content of post-mortem lung material obtained from 15 men who worked in the primary silicon carbide (SiC) industry was evaluated. Five men had neither lung fibrosis nor lung cancer (NFNC), six had lung fibrosis (LF), and four had lung fibrosis and lung cancer (LFLC). The workers had 23 to 32 years of exposure. Mean duration of exposure was 23.4 (SD 6.9) years in the NFNC group, 28.8 (SD 5.5) in the LF, and 32.3 (SD 9.0) in the LFLC group. Concentrations of SiC ceramic fibers and other fibrous minerals and angular particles were determined by transmission electron microscopy and energy dispersive spectroscopy. The geometric mean and geometric standard deviation lung concentrations of SiC ceramic fibers < 5 microns were not statistically different for the three groups (Mann-Whitney, p > 0.1). Pulmonary retention of SiC fibers > or = 5 microns showed an excess in LF and LFLC cases combined versus NFNC that approached statistical significance (Mann-Whitney, p = 0.06). There was a somewhat greater difference for lung retention of ferruginous bodies between NFNC and either LF or LFLC cases (Mann-Whitney, p = 0.02). SiC fibers > or = 5 microns and angular particles containing Si and especially ferruginous bodies were found at higher concentrations in LF and LFLC than in NFNC cases.

Preparation and characterization of ZCAP blends.

Six different blends of zinc oxide, calcium oxide, phosphorous pentoxide (ZCAP) were prepared by mixing zinc oxide (ZnO), calcium oxide (CaO), and phosphorous pentoxide (P2O5) powders. The blends were 50:30:20, 48:32:20, 44:26:30, 40:40:20, 30:40:30, and 30:30:40, ZnO:CaO:P2O5 by weight, respectively. The mixed powders were calcined at 800 degrees C for 12 hours. Each blend was then characterized using X-ray diffraction. The X-ray diffraction patterns indicated that in some cases the reaction between oxides may not have gone to completion. Compositions of beta-3CaO.P2O5 and alpha-CaZn2(PO4)2 were found in many of the blends.