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16 protocols using ingeo biopolymer 4032d

1

Biopolymer-Based Nanocomposite Development

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PLA was a semi-crystalline grade (INGEOTM Biopolymer 4032D) from NatureWorks LLC (Blair, NE, USA), with Mn = 133,000 and molecular weight distribution Mw/Mn =1.9. Other characteristics from the manufacturer were: relative viscosity of 3.94, D stereo-isomer content of 1.4%, and residual monomer content of 0.14%. Commercially-available ZnO-NPs were kindly supplied by SkySpring Nanomaterials Inc (Houston, TX, USA) and were used without further purification. The average diameter specified by the supplier was 20 nm, and the specific surface area 30 to 50 m2/g. A second zinc oxide-based nanoparticle system was used and consisted in ZnO nanodomains embedded in bimodal mesoporous silica. This composite powder, referred to as ZnO-UVM-7, was used with three different Zn content (Si/Zn = 5, 25, and 50), and was produced by the atrane method [50 (link),51 (link),52 (link)]. The final ZnO-UVM-7 material was bimodal and mesoporous with high surface area up to 1000 m2/g. These nanoparticles had a diameter ranging from 2 to 5 nm [50 (link)]. TFE (TFE ≥ 99%) was purchased from Sigma-Aldrich Co.LLC (Oakville, ON, Canada). Cultures of Escherichia coli (E. coli strain DH5α non-pathogen) were obtained from the Laboratory of Microbiology, Infectiology and Immunology (Université de Montréal, Québec, Canada).
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2

PLA Polymer Characterization and Applications

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Commercial polylactic acid (PLA) polymer, IngeoTM biopolymer 4032D, with a melt flow rate (MFR) = 7 g/10 min (210 °C, 2.16 kg) by NatureWorks (Minneapolis, MN, USA), was purchased from a distributor, Suzhou Ziyunxuan Plastic Co., Ltd. (Suzhou, China). Polyethylene glycol (PEG, molecular weight = 2000 g/mol), graphene oxide (2 mg/mL, dispersed in N-methyl pyrrolidone), rosmarinic acid (RosA), dichloromethane (DCM), N,N-dimethylformamide (DMF), sodium chloride, and sodium pentobarbital were all purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).
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3

PLA Polymer Degradation Study

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In order to find a correlation between the polymer’s structure and susceptibility to degradation, different grades of PLA were chosen as the objects of this investigation, namely: Ingeo Biopolymer 2500HP, Ingeo Biopolymer 3100HP, Ingeo Biopolymer 3260HP, and Ingeo Biopolymer 4032D, all of which were supplied by Nature Works (Minnetonka, MN, USA). The chosen properties of the resins are presented in Table 1.
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4

Synthesis of Biodegradable Plastic Blends

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As the biodegradable plastic material PLA (Ingeo™ Biopolymer 4032D, NatureWorks LLC, Minnetonka MN, USA), and PBAT (EnPol PBG7070, Lotte Chemical Co., Seoul, Republic of Korea) were purchased. As the initiators dicumyl peroxide (DCP, Sigma-Aldrich, St. Louis, MO, USA) was purchased, and grafting materials MAH (Sigma-Aldrich, St. Louis, MO, USA) was purchased. Figure 1 shows the molecular structures.
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5

Antimicrobial Polymer-Based Formulations

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Poly(ethylene oxide) (PEO, Badimol-M® Dimitrovgrad, Bulgaria) was used. Its viscosity-average molar mass (600,000 g/mol) was determined in distilled water at 30 °C by Ubbelohde viscometer using the equation: [η] = 1.25 × 10−4 × Mη0.78 [38 ]. Poly(L-lactide) (PLA) was also used (Ingeo™ Biopolymer 4032D, NatureWorks LLC—USA; Mw = 259,000 g/mol; Mw/Mn = 1.94; as determined by size-exclusion chromatography using polystyrene standards). Beeswax with purity corresponding to the European Pharmacopoeia was bought from Chemax Pharma Ltd., Sofia, Bulgaria.; 5-Nitro-8-hydroxyquinoline (NQ) from Sigma-Aldrich (St. Louis, MO, USA); and chloroform, hexane, NaH2PO4 and KH2PO4 from Merck (Darmstadt, Germany). All of the above-mentioned chemicals were reagents for analytical applications and were used as received. Staphylococcus aureus strain 749 (S. aureus), Escherichia coli strain 3588 (E. coli), Candida albicans strain 74 (C. albicans) and Pseudomonas aeruginosa strain 1390 (P. aeruginosa) were supplied by the National Bank for Industrial Microorganisms and Cell Cultures (NBIMCCs), Bulgaria.
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6

PLA/Montmorillonite Composite Fabrication

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A film-grade
polylactic acid, Ingeo biopolymer
4032D, was purchased from NatureWorks Co. Ltd. The selected grade
is a semicrystalline PLA designed for use in the production of food
packaging materials according to the manufacturer’s data sheet.
A commercial montmorillonite organoclay, Cloisite 20A, modified with
a bulky quaternary ammonium salt (dimethyl dihydrogenated tallow ammonium
chloride, 2M2HT) and a modifier concentration of 95 mmol/100 g clay
was supplied by BYK Additives, Germany. Analytical-grade chloroform,
ethanol, hydrochloric acid, and methylene blue were obtained from
Merck GmbH, Germany.
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7

Nanofibrous Membranes from PLGA and PLA

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Experiments were carried out on nanofibrous membranes made of a PLGA copolymer (ratio 85:15, Purasorb® PLG 8531; Corbion, Amsterdam, the Netherlands) or made of PLA (Ingeo™ Biopolymer 4032D; NatureWorks, Minnetonka, MN, USA). The solution for the polymers was prepared and the electrospinning process carried out as presented in our previous work.9 (link) Both polymers were dissolved in chloroform. Solvents – dichloroethane and ethyl acetate – were added into a PLA solution to a final concentration of 7 wt% of PLA. The volume ratio of the chloroform, dichloroethane, and ethyl acetate solvents was 61:29:10. The solution of the two polymers was made electrically conductive with the use of tetraethylammonium bromide. This chemical was first dissolved in dimethylformamide to a concentration of 3 wt%. Then, 3 g of this solution was added to 100 g of the PLGA or PLA solution.
Nanospider needle-free electrospinning technology (Elmarco, Liberec, Czech Republic) was used for preparing the nanofibrous membranes. The process conditions were electrode distance 145–180 mm, voltage 50–60 kV, relative humidity 20%–30%, and room temperature. Fiber density, ie, the area weight of the prepared nanofibers, was 10.5–19.6 g/m2 for PLGA and 13–15 g/m2 for PLA. The thickness of the membranes was in the range of 47–97 μm for PLGA and 125–190 μm for PLA.9 (link)
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8

Electrospinning of PLA Nanofibers

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Poly(l-lactide) (PLA; Ingeo™ Biopolymer 4032D) was purchased from NatureWorks, Minnetonka, MN, USA. The molecular parameters of the polymer material, determined by size exclusion chromatography, were Mw=124,000 g/mol and Mn=48,000 g/mol.39 (link) A 7 wt% solution of PLA in a mixture of chloroform, dichloroethane, and ethyl acetate in the volume ratio of 61:29:10 was used for the electrospinning process. The polymer was diluted only in chloroform, and the other two solvents were added after the dilution. The polymer solution was made electrically conductive with the use of tetraethylammonium bromide, which was first dissolved in dimethylformamide at a concentration of 3 wt%, and then 3 g of this solution was added to 100 g of the PLA solution.40 (link)
Nanofibrous membranes were prepared using the novel Nanospider needleless electrospinning technology (NS Lab 500; Elmarco Ltd., Liberec, Czech Republic). The process conditions were: electrode distance: 180 mm; voltage: 60–10 kV; the spinning electrode rotated at 4 rpm; relative humidity: 25%–30%, and room temperature. The fiber density, ie, the area weight of the prepared nanofibers, was from 12 to 15 g/m2.
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9

PLA-PEG Filament Fabrication Protocol

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The organic backbone in the filaments was a poly(lactic acid) (PLA) named Ingeo Biopolymer 4032D (NatureWorks, Blair, NE, USA). PLA was chosen because it is a bio-based material and is a common material in FFF. Three different polymer blends were studied, (see Section 2.1.3), pure PLA and two blends containing different fractions of poly(ethylene glycole) (PEG) named PEG 3000 (Merck Group, Darmstadt, Germany). PEG was selected as a water-soluble component to allow two-stage debinding. The molecular weight of the used PLA was 107,296 g/mol and 3000 g/mol for the PEG. Before compounding the PLA and the PEG were dried in vacuum for 24 h, the temperatures for drying were 50 °C for PLA and 30 °C for PEG, respectively.
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10

PLA-Based Biopolymer Formulations with Plasticizers

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PLA (Ingeo™ Biopolymer 4032D) was obtained from NatureWorks LLC (Minnetonka, MN, USA). The melt flow index (MFI) of PLA was determined at 6.0 g/10 min at 190 °C. The load was 2.16 kg and the d-lactic acid content was estimated at 2%. PBAT (EnPol PBG7070) was supplied by Lotte Fine Chemical (Seoul, Korea). Adipate (bis[2–(2–butoxyethoxy)ethyl] adipate) was obtained from Sigma-Aldrich (St. Louis, MO, USA). Adipic acid (EDENOL® 1208) and glycerol ester (LOXIOL® P1141) were purchased from Emery Oleochemicals (Telok Panglima Garang, Malaysia). Adipic acid ester (DAIFATTY®-101) was obtained from Daihachi Chemical Industry Co., Ltd. (Osaka, Japan). The aforementioned reagents were used as plasticizers for PLA and their properties are summarized in Table 1. Talc (KCM-6300, KOCH, Seocheon, Korea) and ethylene bis-stearamide wax (HI-LUBETM bead, Sinwon Chemical, Siheung, Korea) were employed as commercial-grade processing aids to reduce the surface friction of films and promote the usage of antiblocking and nucleating agents.
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