The “Superlubricity State” of Carbonaceous Fillers on Polymer Composites

In 2019 Ferreira et al. observed for the first time the influence of the superlubricity phenomenon of platelet‐like fillers on the properties of high molecular weight polyethylene (HMWPE) in the molten state. At the time, the study was carried out in the solid state of the polymer, analyzing the influence of the superlubricity phenomenon of oxide graphene and oxide graphite (GrO) agglomerates on the mechanical properties of the HMWPE. It was observed that the agglomerates, due to their superlubricity state, toughen the HMWPE polymer matrix. Here, mechanical tests (tensile), X‐ray microtomography, and scanning electron microscopy are carried out to elucidate this phenomenon. The same is observed for polystyrene containing very poorly dispersed GrO. The results presented here are a paradigm shift, as it has always been thought that the presence of agglomerates is harmful, but the opposite is proven here. In general, this paper can contribute a lot to the development of new composites and nanocomposites based on fillers that present the superlubricity phenomenon.     

Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents

ObjectivesPhotopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS).MethodsOur system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode.ResultsUsing our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization.SignificanceThe present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites.     

Effect of temperature on composite polymerization stress and degree of conversion

Objective

To test the following hypotheses: (1) degree of conversion (DC) and polymerization stress (PS) increase with composite temperature (2) reduced light-exposure applied to pre-heated composites produces similar conversion as room temperature with decreased PS.

Methods

Composite specimens (diameter: 5 mm, height: 2 mm) were tested isothermally at 22 °C (control), 40 °C, and 60 °C using light-exposures of 5 or 20 s (control). DC was accessed 5 min after light initiation by FTIR at the specimen bottom surface. Maximum and final PS were determined, also isothermally, for 5 min on a universal testing machine. Non-isothermal stress was also measured with composite maintained at 22 °C or 60 °C, and irradiated for 20 s at 30 °C. Data were analyzed using two-way ANOVA/Tukey and Student's t-test (α = 5%).

Results

Both DC and isothermal maximum stress increased with temperature (p < 0.001) and exposure duration (p < 0.001). Isothermal maximum/final stress (MPa) were 3.4 ± 2.0b/3.4 ± 2.0A (22 °C), 3.7 ± 1.5b/3.6 ± 1.4A (40 °C) and 5.1 ± 2.0a/4.0 ± 1.6A (60 °C). Conversion values (%) were 39.2 ± 7.1c (22 °C), 50.0 ± 5.4b (40 °C) and 58.5 ± 5.7a (60 °C). The reduction of light exposure duration (from 20 s to 5 s) with pre-heated composite yielded the same or significantly higher conversion (%) than control (22 °C, 20 s/control: 45.4 ± 1.8b, 40 °C, 5 s s: 45.1 ± 0.5b, 60 °C, 5 s s: 53.7 ± 2.7a, p < 0.01). Non-Isothermal conditions showed significantly higher stress for 60 °C than 22 °C (in MPa, maximum: 4.7 ± 0.5 and 3.7 ± 0.4, final: 4.6 ± 0.6 and 3.6 ± 0.4, respectively).Clinical significance: Increasing composite temperature allows for reduced exposure duration and lower polymerization stress (both maximum and final) while maintaining or increasing degree of conversion.     

Reduced polymerization stress of MAPO-containing resin composites with increased curing speed,degree of conversion and mechanical properties

Objectives

The degree and rate of photopolymerization in resin-based dental composites will significantly affect polymer network formation and resultant material properties that may determine their clinical success. This study investigates the mechanical properties, the generation of stress from polymerization, tooth cusp deflection and marginal integrity of experimental resin composites that contain different photoinitiators.

Methods

Experimental light-activated resin composites (60 vol% particulate filled in 50/50 mass% bis-GMA/TEGDMA) were formulated using a monoacylphosphine oxide (MAPO) photoinitiator and compared with a conventional camphoroquinone (CQ)-based system. Similar radiant exposure was used (18 J cm⁻²) for polymerization of each material although the curing protocol was varied (400 mW cm⁻² for 45 s, 1500 mW cm⁻² for 12 s and 3000 mW cm⁻² for 6 s). Degree and rate of polymerization was calculated in real-time by near infrared spectroscopy and the generation of stress throughout polymerization measured using a cantilever beam method. Flexural strength and modulus were acquired by three-point bend tests. Standardized cavities in extract pre-molar teeth were restored with each material, the total cuspal deflection measured and post-placement marginal integrity between the tooth and restoration recorded.

Results

Generally, MAPO- exhibited a significantly higher degree of conversion (72 ± 0.8 to 82 ± 0.5%) compared with CQ-based materials (39 ± 0.7 to 65 ± 1.6%) regardless of curing protocol (p < 0.05) and MAPO-based materials exhibited less difference in conversion between curing protocols. CQ-based materials exhibited between ∼85 and 95% of the maximum rate of polymerization at <15% conversion, whereas MAPO-based RBCs did not approach the maximum rate until >50% conversion. Higher irradiance polymerization had a significant deleterious effect on the mechanical properties of CQ-based materials (p < 0.05) whereas MAPO-based materials exhibited increased strength and modulus and were less affected by the curing method. Total cuspal deflection in restored extracted teeth was higher for CQ- compared with MAPO-based materials cured at the lowest irradiance curing protocol (12.9 ± 4.0 and 8.3 ± 1.5 μm) and similar at 3000 mW cm⁻¹ for 6 s (10.1 ± 3.5 and 9.0 ± 1.5 μm). A significant decrease in marginal integrity was observed for CQ-based RBCs cured at high irradiance for short exposure time compared with that of the MAPO-based RBC cured using a similar protocol (p = 0.037).

Significance

Polymer network formation dictates the final properties of the set composite and the use MAPO photoinitiators may provide an effective restorative material that exhibits higher curing speeds, increased degree of conversion, strength and modulus without compromise in terms of polymerization stress and marginal integrity between tooth and restoration.     

Post-cure depth of cure of bulk fill dental resin-composites

Objectives

To determine the post-cure depth of cure of bulk fill resin composites through using Vickers hardness profiles (VHN).

Methods

Five bulk fill composite materials were examined: Tetric EvoCeram^® Bulk Fill, X-tra base, Venus^® Bulk Fill, Filtek™ Bulk Fill, SonicFill™. Three specimens of each material type were prepared in stainless steel molds which contained a slot of dimensions (15 mm × 4 mm × 2 mm), and a top plate. The molds were irradiated from one end. All specimens were stored at 37 °C for 24 h, before measurement. The Vickers hardness was measured as a function of depth of material, at 0.3 mm intervals. Data were analysed by one-way ANOVA using Tukey post hoc tests (α = 0.05).

Results

The maximum VHN ranged from 37.8 to 77.4, whilst the VHN at 80% of max.VHN ranged from 30.4 to 61.9. The depth corresponding to 80% of max.VHN, ranged from 4.14 to 5.03 mm. One-way ANOVA showed statistically significant differences between materials for all parameters tested. SonicFill exhibited the highest VHN (p < 0.001) while Venus Bulk Fill the lowest (p ≤ 0.001). SonicFill and Tetric EvoCeram Bulk Fill had the greatest depth of cure (5.03 and 4.47 mm, respectively) and was significant's different from X-tra base, Venus Bulk Fill and Filtek Bulk Fill (p ≤ 0.016). Linear regression confirmed a positive regression between max.VHN and filler loading (r² = 0.94).

Significance

Bulk fill resin composites can be cured to an acceptable post-cure depth, according to the manufacturers’ claims. SonicFill and Tetric EvoCeram Bulk Fill had the greatest depth of cure among the composites examined.     

Do nanofill or submicron composites show improved smoothness and gloss? A systematic review of in vitro studies

Objectives

Despite nanofill and submicron composites’ aim to provide high initial polishing combined with superior smoothness and gloss retention, the question still remains whether clinicians should consider using these new materials over traditional microhybrids. The aim of this paper was to systematically review the literature on how nanofills and submicrons react to polishing procedures and surface challenges in vitro compared with microhybrids. The paper has also given an overview of the compositional characteristics of all resin composites and polishing systems whose performance was presented herein.

Data

The database search for the effect of filler size on surface smoothness and gloss of commercial composites retrieved 702 eligible studies. After deduplication, 438 records were examined by the titles and abstracts; 400 studies were excluded and 38 articles were assessed for full-text reading. An additional 11 papers were selected by hand-searching. In total, 28 articles met inclusion criteria and were included in the study.

Sources

The databases analyzed were MEDLINE/PubMed, ISI Web of Science, and SciVerse Scopus.

Study selection

Papers were selected if they presented a comparison between nanofill or submicron and microhybrid composites with quantitative analysis of smoothness and/or gloss on baseline and/or after any aging protocol to assess smoothness and gloss retention. Only in vitro studies written in English were included.

Conclusions

There is no in vitro evidence to support the choice for nanofill or submicron composites over traditional microhybrids based on better surface smoothness and/or gloss, or based upon maintenance of those superficial characteristics after surface challenges.     

异种脱细胞真皮移植联合自体刃厚皮片移植修复手部深度烧伤创面

目的探讨异种脱细胞真皮(s-ADM)移植联合自体刃厚皮片(auto-OTS)移植修复手部深度烧伤创面的效果。方法选取2017年2月~2019年8月我院手部深度烧伤患者72例,依据随机数字表法分组,各36例。常规治疗基础上,对照组采用auto-OTS移植治疗,研究组在对照组基础上采用s-ADM移植治疗。比较两组创面细菌量、皮片存活率、创面愈合时间、手部功能优良率、温哥华瘢痕量表(VSS)评分、术后并发症发生率。结果研究组皮片存活率94.44%高于对照组77.78%,创面细菌量少于对照组,创面愈合时间短于对照组(P<0.05);研究组手部功能优良率91.67%高于对照组72.22%,VSS评分低于对照组,术后并发症发生率5.56%低于对照组25.00%(P<0.05)。结论 s-ADM移植联合auto-OTS移植修复手部深度烧伤创面,可减少创面细菌量,提高皮片存活率,促进创面愈合,提高手部功能优良率,减轻瘢痕增生,且安全性高。     

Effect of Electroless Cu Plating Ti3AlC2 Particles on Microstructure and Properties of Gd2O3/Cu Composites

Ti₃AlC₂ presents a hexagonal layered crystal structure and bridges the gap between metallic and ceramic properties, and Gadolinia (Gd₂O₃) has excellent thermodynamic stability, which make them potentially attractive as dispersive phases for Cu matrix composites. In this paper, Cu@Ti₃AlC₂-Gd₂O₃/Cu composites, Ti₃AlC₂-Gd₂O₃/Cu composites, and Gd₂O₃/Cu composites were prepared by electroless Cu plating, internal oxidation, and vacuum hot press sintering. The microstructure and the effect of the Cu plating on the properties of the Cu@Ti₃AlC₂-Gd₂O₃/Cu composites were discussed. The results showed that a Cu plating with a thickness of about 0.67 μm was successfully plated onto the surface of Ti₃AlC₂ particles. The ex situ Ti₃AlC₂ particles were distributed at the Cu grain boundary, while the in situ Gd₂O₃ particles with a grain size of 20 nm were dispersed in the Cu grains. The electroless Cu plating onto the surface of the Ti₃AlC₂ particles effectively reduces their surfactivity and improves the surface contacting state between the Cu@Ti₃AlC₂ particles and the Cu matrix, and reduces electron scattering, so that the tensile strength reached 378.9 MPa, meanwhile, the electrical conductivity and elongation of the Cu matrix composites was maintained at 93.6 IACS% and 17.6%.     

Combustion Synthesis of High Density ZrN/ZrSi2 Composite: Influence of ZrO2 Addition on the Microstructure and Mechanical Properties

In this study, a high-density ZrN/ZrSi₂ composite reinforced with ZrO₂ as an inert phase was synthesized under vacuum starting with a Zr-Si₄N₃-ZrO₂ blend using combustion-synthesis methodology accompanied by compaction. The effects of ZrO₂ additions (10–30 wt%) and compression loads (117–327 MPa) on the microstructure, porosity and hardness of the samples were studied. The process was monitored using XRD, SEM, EDS, porosity, density and hardness measurements. Thermodynamic calculations of the effect of ZrO₂ addition on the combustion reaction were performed including the calculation of the adiabatic temperatures and the estimation of the fractions of the liquid phase. The addition of up to 20 wt% ZrO₂ improved the hardness and reduced the porosity of the samples. Using 20 wt% ZrO₂, the sample porosity was reduced to 1.66 vol%, and the sample hardness was improved to 1165 ± 40.5 HV at 234 MPa.     

The Influence of Low-Molecular-Weight Monomers (TEGDMA,HDDMA, HEMA) on the Properties of Selected Matrices and Composites Based on Bis-GMA and UDMA

Bisphenol A-glycidyl methacrylate (bis-GMA) and urethane dimethacrylate (UDMA) are usually combined with low-viscosity monomers to obtain more desirable viscosity, handling characteristics and general properties. The present study determined the flexural strength (FS), flexural modulus (FM), diametral tensile strength (DTS), and hardness (HV) of five matrices and composites based on these resins. The polymerization shrinkage stress (PSS) was also studied for the composites. The polymer matrices were formed using bis-GMA and UDMA. TEGDMA, HEMA and HDDMA acted as co-monomers. The composites had 45 wt.% of filler content. The highest FS and FM were obtained from the UDMA/bis-GMA/TEGDMA/HEMA matrix and the composite (matrix + filler). The best DTS values were obtained from the UDMA/bis-GMA/HEMA matrix and the composite. One of the lowest values of FS, FM, and DTS was obtained from the UDMA/bis-GMA/HDDMA matrix and the composite. All the composites demonstrated similar hardness values. The lowest polymerization shrinkage stress was observed for the UDMA/bis-GMA/TEGDMA/HEMA composite, and the highest PSS was observed for the UDMA/bis-GMA/TEGDMA/HDDMA composite. The addition of HEMA had a positive effect on the properties of the tested materials, which may be related to the improved mobility of the bis-GMA and UDMA monomers.