scholarly journals Effects of Two Melt Extrusion Based Additive Manufacturing Technologies and Common Sterilization Methods on the Properties of a Medical Grade PLGA Copolymer

Polymers ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 572
Author(s):  
Marion Gradwohl ◽  
Feng Chai ◽  
Julien Payen ◽  
Pierre Guerreschi ◽  
Philippe Marchetti ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Additive Manufacturing ◽  
Ethylene Oxide ◽  
Medical Devices ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Fused Filament Fabrication ◽  
Scanning Calorimetry ◽  
Manufacturing Technologies ◽  
Medical Grade

Although bioabsorbable polymers have garnered increasing attention because of their potential in tissue engineering applications, to our knowledge there are only a few bioabsorbable 3D printed medical devices on the market thus far. In this study, we assessed the processability of medical grade Poly(lactic-co-glycolic) Acid (PLGA)85:15 via two additive manufacturing technologies: Fused Filament Fabrication (FFF) and Direct Pellet Printing (DPP) to highlight the least destructive technology towards PLGA. To quantify PLGA degradation, its molecular weight (gel permeation chromatography (GPC)) as well as its thermal properties (differential scanning calorimetry (DSC)) were evaluated at each processing step, including sterilization with conventional methods (ethylene oxide, gamma, and beta irradiation). Results show that 3D printing of PLGA on a DPP printer significantly decreased the number-average molecular weight (Mn) to the greatest extent (26% Mn loss, p < 0.0001) as it applies a longer residence time and higher shear stress compared to classic FFF (19% Mn loss, p < 0.0001). Among all sterilization methods tested, ethylene oxide seems to be the most appropriate, as it leads to no significant changes in PLGA properties. After sterilization, all samples were considered to be non-toxic, as cell viability was above 70% compared to the control, indicating that this manufacturing route could be used for the development of bioabsorbable medical devices. Based on our observations, we recommend using FFF printing and ethylene oxide sterilization to produce PLGA medical devices.

Binary molybdenum-based catalyst for coordination polymerization of styrene

2016 ◽  
Vol 49 (5) ◽  
pp. 408-421 ◽  
Author(s):  
Jieting Geng ◽  
Youguo Shao ◽  
Feng Song ◽  
Feng Li ◽  
Jing Hua
Keyword(s):  
Molecular Weight ◽  
Catalyst Activity ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Catalyst System ◽  
Bulk Polymerization ◽  
Molar Ratio ◽  
Scanning Calorimetry ◽  
Coordination Polymerization ◽  
Co Catalyst

Coordination polymerization of styrene (St) using molybdenum pentachloride supported by phosphite ligand in the presence of metal organic compound was studied for the first time. The types of phosphite and co-catalysts significantly affected the catalytic activity of the molybdenum (V) (Mo(V)) active center and the number-average molecular weight ( Mn) of the resultant polymer. Among the examined catalysts, tri(nonylphenyl)phosphite (TNPP) ligand and AlOPhCH3( i-Bu)2 as co-catalyst provided the polymer with highest yield (up to 87.1%), metallocene as co-catalyst provided the polymer with highest Mn (up to 5.32 × 105). The effect of [P]/[Mo] molar ratio on catalyst activity of the polymerization was discussed and the structures of Mo·TNPP complexes were preliminarily studied by infrared (IR) and ultraviolet spectroscopies. Besides, the polystyrene (PS) samples synthesized through bulk polymerization and solution polymerization were characterized by gel permeation chromatography, IR, carbon 13 nuclear magnetic resonance, and differential scanning calorimetry, respectively, and the results indicated both of the PS had high molecular weight (approximately 105) and atactic structure. All these results demonstrated that Mo(V) catalyst system was very effective for St polymerization.

On the structure alteration of crosslinkable gelatin coupled with methacrylic acid and its hydrogel

e-Polymers ◽  
2012 ◽  
Vol 12 (1) ◽  
Author(s):  
Xiaohong Hu ◽  
Dan Li ◽  
Feng Zhou ◽  
Changyou Gao
Keyword(s):  
Molecular Weight ◽  
Triple Helix ◽  
Sol Gel ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Apparent Molecular Weight ◽  
Small Range ◽  
Scanning Calorimetry ◽  
Physical Chemical ◽  
Substitution Degree

AbstractPhysical structures of a crosslinkable gelatin derivative (GM) were studied in terms of alteration of apparent molecular weight, triple helix content and mechanical strength. The GM with a substitution degree (DS) of 49% and 79% was prepared by grafting mechacrylic acid (MA), which was able to form injectable hydrogel by photoinitiating polymerization. The zeta potential was increased along the increase of DS. After modification, the apparent number-average molecular weight (Mn) detected by gel permeation chromatography was decreased to about 2/3 of gelatin, while the apparent weight-average molecular weight (Mw) was changed within a small range. Differential scanning calorimetry and circular dichroism (CD) revealed that ability of triple-helix formation of GM was decreased along with the increase of DS and decrease of GM concentration. After photocrosslinking, the sol-gel transition of GM49 physical-chemical hydrogel still existed, but completely disappeared for its chemical hydrogel. The physical-chemical hydrogel showed a larger storage modulus at 20°C than at 37°C as a result of additional physical crosslinking.

scholarly journals Are Medical Grade Bioabsorbable Polymers a Viable Material for Fused Filament Fabrication?

2019 ◽  
Vol 13 (3) ◽  
Author(s):  
Jaclyn Schachtner ◽  
Michael Frohbergh ◽  
Noreen Hickok ◽  
Steven Kurtz
Keyword(s):  
Lumbar Fusion ◽  
Dimensional Accuracy ◽  
Gel Permeation Chromatography ◽  
Raw Material ◽  
Fused Filament Fabrication ◽  
Scanning Calorimetry ◽  
Polyether Ether Ketone ◽  
The Cost ◽  
Degradation Properties ◽  
Medical Grade

Lumbar fusion surgery has grown in popularity as a solution to lower back pain. Surgical site infection (SSI) is a serious complication of spinal surgery, affecting as high as 8.5% of the patient population. If the SSI cannot be eradicated with intravenous antibiotics, the next step is second surgery, which increases the cost imposed on the patient and extends recovery time. An implantable ultrasound-triggered polyether ether ketone device for the dispersal of antibiotics has been developed as a potential solution. In this study, the device was constructed of bioabsorbable medical grade polymer, enabling gradual degradation, and manufactured via fused filament fabrication (FFF). A novel bioabsorbable filament was manufactured and validated with gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The filament was consistent in molecular weight and thermal properties (p = 0.348 and p = 0.487, respectively). The filament was utilized for FFF of the device. Dimensional accuracy of the device was assessed with μCT analysis. Dimensional differences between the printed device and intended design were minimal. Degradation of raw material, filament, and the device was performed in accordance to ASTM F1635-16 for a month to determine how melting the material impacted the degradation properties. The degradation rate was found to be similar among the samples weeks one through three however, the raw material degraded at a slower rate by the final week (p = 0.039). This study demonstrated the feasibility of utilizing medical grade bioabsorbable polymers in FFF.

The Structure of Radiation Cross-Linked Poly (ethylene oxide) Gels

1971 ◽  
Vol 29 ◽  
pp. 76-77
Author(s):  
C. E. Cluthe ◽  
G. G. Cocks
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Parallel Plate ◽  
Average Molecular Weight ◽  
Radical Reaction ◽  
Free Radical Reaction ◽  
Nitrogen Gas ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Initial Viscosity

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.

scholarly journals Metallization of Thermoplastic Polymers and Composites 3D Printed by Fused Filament Fabrication

Technologies ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 49
Author(s):  
Alessia Romani ◽  
Andrea Mantelli ◽  
Paolo Tralli ◽  
Stefano Turri ◽  
Marinella Levi ◽  
...  
Keyword(s):  
Physical Vapor Deposition ◽  
Test Sample ◽  
Tensile Tests ◽  
Layer By Layer ◽  
Post Processing ◽  
Thermoplastic Polymers ◽  
Fused Filament Fabrication ◽  
Scanning Calorimetry ◽  
3D Printed ◽  
Manufacturing Technologies

Fused filament fabrication allows the direct manufacturing of customized and complex products although the layer-by-layer appearance of this process strongly affects the surface quality of the final parts. In recent years, an increasing number of post-processing treatments has been developed for the most used materials. Contrarily to other additive manufacturing technologies, metallization is not a common surface treatment for this process despite the increasing range of high-performing 3D printable materials. The objective of this work is to explore the use of physical vapor deposition sputtering for the chromium metallization of thermoplastic polymers and composites obtained by fused filament fabrication. The thermal and mechanical properties of five materials were firstly evaluated by means of differential scanning calorimetry and tensile tests. Meanwhile, a specific finishing torture test sample was designed and 3D printed to perform the metallization process and evaluate the finishing on different geometrical features. Furthermore, the roughness of the samples was measured before and after the metallization, and a cost analysis was performed to assess the cost-efficiency. To sum up, the metallization of five samples made with different materials was successfully achieved. Although some 3D printing defects worsened after the post-processing treatment, good homogeneity on the finest details was reached. These promising results may encourage further experimentations as well as the development of new applications, i.e., for the automotive and furniture fields.

Probing the molecular weights of sweetgum and pine kraft lignin fractions

TAPPI Journal ◽  
2021 ◽  
Vol 20 (6) ◽  
pp. 381-391
Author(s):  
JULIANA M. JARDIM ◽  
PETER W. HART ◽  
LUCIAN LUCIA ◽  
HASAN JAMEEL
Keyword(s):  
Molecular Weight ◽  
Black Liquor ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Systematic Investigation ◽  
Kraft Pulping ◽  
Molecular Weights ◽  
Lignin Recovery ◽  
Lignin Reactivity ◽  
Kinetics Of

The present investigation undertook a systematic investigation of the molecular weight (MW) of kraft lignins throughout the pulping process to establish a correlation between MW and lignin recovery at different extents of the kraft pulping process. The evaluation of MW is crucial for lignin characterization and utilization, since it is known to influence the kinetics of lignin reactivity and its resultant physicochemical properties. Sweetgum and pine lignins precipitated from black liquor at different pHs (9.5 and 2.5) and different extents of kraft pulping (30–150 min) were the subject of this effort. Gel permeation chromatography (GPC) was used to deter- mine the number average molecular weight (Mn), mass average molecular weight (Mw), and polydispersity of the lignin samples. It was shown that the MW of lignins from both feedstocks follow gel degradation theory; that is, at the onset of the kraft pulping process low molecular weightlignins were obtained, and as pulping progressed, the molecular weight peaked and subsequently decreased. An important finding was that acetobromination was shown to be a more effective derivatization technique for carbohydrates containing lignins than acetylation, the technique typically used for derivatization of lignin.

scholarly journals Characterisation of Sequential Solvent Fractionation and Base-catalysed Depolymerisation of Treated Alkali Lignin

BioResources ◽  
2015 ◽  
Vol 10 (3) ◽  
pp. 4137-4151 ◽  
Author(s):  
Aikfei Ang ◽  
Zaidon Ashaari ◽  
Edi Suhaimi Bakar ◽  
Nor Azowa Ibrahim
Keyword(s):  
Molecular Weight ◽  
Chemical Structure ◽  
Average Molecular Weight ◽  
Gel Permeation Chromatography ◽  
Solubility Parameters ◽  
Low Molecular Weight ◽  
Sequential Fractionation ◽  
Weight Average Molecular Weight ◽  
Solvent Fractionation ◽  
Alkali Lignin

An alkali lignin (OL) with a weight-average molecular weight (Mw) of 11646 g/mol was used to prepare low-molecular weight lignin for resin synthesis. The low-molecular weight lignin feedstock was obtained via base-catalysed depolymerisation (BCD) treatments at different combined severity factors. Sequential fractionation of the OL and BCD-treated lignins using organic solvents with different Hildebrand solubility parameters were used to alter the homogeneity of the OL. The yield and properties of OL itself and OL and BCD-treated OL dissolved in propan-1-ol (F1), ethanol (F2), and methanol (F3) were determined. Regardless of the treatment applied, a small amount of OL was dissolved in F1 and F2. The BCD treatment did not increase the yield of F1 but did increase the yields of F2 and F3. Gel permeation chromatography (GPC) showed that the repolymerization reaction occurred in F3 for all BCD-treated OL, so these lignins were not suitable for use as feedstocks for resin production. The GPC, 13Carbon-nuclear magnetic resonance, and Fourier transform infrared spectroscopy analyses confirmed that the F3 in OL exhibited the optimum yield, molecular weight distribution, and chemical structure suitable for use as feedstocks for resin synthesis.

Characterization of bi-layered magnetic nanoparticles synthesized via two-step surface-initiated ring-opening polymerization

2015 ◽  
Vol 87 (11-12) ◽  
pp. 1085-1097 ◽  
Author(s):  
Li Wang ◽  
Stefan Baudis ◽  
Karl Kratz ◽  
Andreas Lendlein
Keyword(s):  
Magnetic Nanoparticles ◽  
Ring Opening ◽  
Average Molecular Weight ◽  
Polymer Networks ◽  
Gel Permeation Chromatography ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
H Nmr ◽  
Transmission Electron

AbstractA versatile strategy to integrate multiple functions in a polymer based material is the formation of polymer networks with defined nanostructures. Here, we present synthesis and comprehensive characterization of covalently surface functionalized magnetic nanoparticles (MNPs) comprising a bi-layer oligomeric shell, using Sn(Oct)2 as catalyst for a two-step functionalization. These hydroxy-terminated precursors for degradable magneto- and thermo-sensitive polymer networks were prepared via two subsequent surface-initiated ring-opening polymerizations (ROPs) with ω-pentadecalactone and ε-caprolactone. A two-step mass loss obtained in thermogravimetric analysis and two distinct melting transitions around 50 and 85°C observed in differential scanning calorimetry experiments, which are attributed to the melting of OPDL and OCL crystallites, confirmed a successful preparation of the modified MNPs. The oligomeric coating of the nanoparticles could be visualized by transmission electron microscopy. The investigation of degrafted oligomeric coatings by gel permeation chromatography and 1H-NMR spectroscopy showed an increase in number average molecular weight as well as the presence of signals related to both of oligo(ω-pentadecalactone) (OPDL) and oligo(ε-caprolactone) (OCL) after the second ROP. A more detailed analysis of the NMR results revealed that only a few ω-pentadecalactone repeating units are present in the degrafted oligomeric bi-layers, whereby a considerable degree of transesterification could be observed when OPDL was polymerized in the 2nd ROP step. These findings are supported by a low degree of crystallinity for OPDL in the degrafted oligomeric bi-layers obtained in wide angle X-ray scattering experiments. Based on these findings it can be concluded that Sn(Oct)2 was suitable as catalyst for the preparation of nanosized bi-layered coated MNP precursors by a two-step ROP.

Synthesis of Segmented Anisotropic-Isotropic Poly(Aryl Ester)Poly(Arylene Ether) Copolymers

1989 ◽  
Vol 175 ◽  
Author(s):  
J. E. McGratn ◽  
K. L. Cooper ◽  
W. Waehamad ◽  
H. Huang ◽  
G. L. Wilkes
Keyword(s):  
Molecular Weight ◽  
Liquid Crystal ◽  
Benzoic Acid ◽  
Liquid Crystalline ◽  
Average Molecular Weight ◽  
Nucleophilic Aromatic Substitution ◽  
Copolymer Composition ◽  
Aromatic Substitution ◽  
Scanning Calorimetry ◽  
Arylene Ether

AbstractCarboxyl functional poly(arylene ether) oligomers of controlled number average molecular weight were synthesized via nucleophilic aromatic substitution step polymerization using p-hydroxy benzoic acid as the molecular weight and end group controlling reagents. The subsequent functionalized polyarylene ethers were copolymerized with acetoxy benzoic acid or acetoxyphenoxy benzoic acid via melt acidolysis procedures. Successful copolymers were generated using chlorobenzene as a solvent for the first s age of the reaction followed by melt reaction at temperatures as high as 325°C. Resulting copolymer composition and segment size were investigated. It was possible to prepare improved solvent resistant copolymers through incorporation of the liquid crystal polyester (LCP) segment. Extraction tests using boiling chloroform showed that a high percentage of segmented copolymer were generated. Swelling characteristics were also noted and were observed to decrease as a function of the LCP concentration utilized. Multiple transitions were observed in differential scanning calorimetry consistent with Tg's, Tm's and possibly with liquid crystal transitions. Optical microscopy showed an ordered microstructure developed which is consistent with the presence of liquid crystalline phases. The materials were successfully compression molded to afford tough coherent films at all compositions, implying the likelihood of improved compressive strength relative to the LCP homo- or copolyesters.

scholarly journals Poly(lactic acid) polymer stars built from early generation dendritic polyols

2013 ◽  
Vol 91 (6) ◽  
pp. 392-397 ◽  
Author(s):  
Genny E. Keefe ◽  
Jean-d'Amour K. Twibanire ◽  
T. Bruce Grindley ◽  
Michael P. Shaver
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Gel Permeation Chromatography ◽  
Poly Lactic Acid ◽  
Reactive Site ◽  
Scanning Calorimetry ◽  
Early Generation ◽  
Sequential Reaction ◽  
Cyclic Esters ◽  
Total Molecular Weight

A family of polymer stars has been prepared from early generation dendritic cores with four, six, and eight arms. Four dendritic cores were prepared from the sequential reaction of a multifunctional alcohol with a protected anhydride, followed by deprotection to afford two or three new alcohol functionalities per reactive site. These cores were used as initiators for the tin-catalyzed ring-opening polymerization of l-lactide and rac-lactide to afford isotactic and atactic degradable stars, respectively. Two series of stars were prepared for each monomer, either maintaining total molecular weight or number of monomer units per arm. The polymers were characterized by NMR spectroscopy, light-scattering gel-permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis. Our results support previous work that suggests that the length of the arms dictates thermal properties rather than the total molecular weight of the star. Little effect was noted between aromatic and aliphatic cores, presumably due to the flexibility of the rest of the core molecule. We have shown that early generation dendrimers can serve as excellent core structures for building core-first polymer stars via the ring-opening of cyclic esters.

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