Hybrid biopolymer composites for 3D printing applications

Předkládaná práce popisuje termické a mechanické chování změkčených bio-plastů a bio-kompozitů se zaměřením na použití v 3D tisku. Zkoumán byl vliv chemické struktury změkčovadla na bázi derivátů kyseliny citronové na termické a mechanické vlastnosti vzorků změkčené polymerní směsi poly-3-hydroxybutyrátu a kyseliny polymléčné. Vliv změkčovadla na polymerní matrici a jejich vzájemná kompatibilita byla posuzována rychlostí zamísení změkčovadla do taveniny, respektive rychlostí migrace změkčovadla ven z materiálu za zvýšené teploty. Pomocí modulované diferenciální skenovací kalorimetrie byl sledován vliv struktury změkčovadla na teplotu skelného přechodu a krystalizační kinetiku změkčeného materiálu. Sledováno bylo také chování materiálu při 3D tisku. Pomocí tahové zkoušky byly stanoveny mechanické vlastnosti tištěných těles, především jejich tažnost. Nejvyšší efekt změkčení byl pozorován za použití změkčovadla tributylcitrátu, kdy bylo dosaženo poklesu teploty skelného přechodu o a zvýšení tažnosti o 150 % oproti neměkčené referenci. Takto změkčená polymerní směs vykazovala i dostatečné 3D tiskové vlastnosti a byla využita jako matrice pro kompozity v další části práce. Kompozity byly plněny kaolinem, vápencem, halloysitem, sráženou silikou, mastkem, hydroxidem hořečnatým a sekaným lněným vláknem. U kompozitů byla sledována distribuce částic pomocí skenovací elektronové mikroskopie v závislosti na použití povrchové úpravy plniva. Pomocí viskozimetrie a diferenciální skenovací kalorimetrie byl u kompozitů sledován vliv plniva na reologické chování, krystalizační kinetiku a termickou stabilitu kompozitů. Jejich mechanické vlastnosti a teplota průhybu při zatížení byly sledovány na tělesech připravených 3D tiskem. Kaolin vykazoval v kompozitním materiálu homogenní distribuci částic a zanedbatelný vliv na termickou stabilitu a nukleaci matrice. Kaolinem plněný kompozit navíc vykazoval oproti neplněné referenci o 18 % menší warping při tisku, proto byl kaolin vyhodnocen jako vhodné plnivo pro bioplastové kompozity určené pro 3D tisk a tento kompozit je využíván v další kapitole práce. Pro kompozitní vzorky připravené 3D tiskem byla popsána metoda matematické predikce modulu pružnosti. Kompozity plněné jedním typem plniva - kaolinem, nebo vápencem, respektive kombinací obou plniv byly zkoumány na základě úpravy mikromechanického modelu Halpin-Tsai semiempirickou multiparametrickou Černého rovnicí. Pro kompozity s hybridním plněním je prezentována aditivní a kombinační metoda výpočtu modulu pružnosti. Zavedenou korekcí byla snížena odchylka naměřené a teoretické hodnoty modulu pružnosti kompozitu plněného kaolinem z 21 % na 1 % a kompozitu plněného kaolinem a vápencem z 13 % na 9 %. Tímto přístupem je možno předpovědět modul pružnosti materiálů ze vzorků připravených 3D tiskem.This dissertation work deals with the thermic and the mechanical behavior of plasticized bio-plastics and bio-composites for the 3D printing applications. The influence of plasticizer chemical structure on thermic and mechanical properties of plasticized polymeric blends from the poly-3-hydroxybutyrate and the poly lactic acid was investigated. Used plasticizers are based on derivative of citric acid. The influence of plasticizers on polymeric matrix and their compatibility was estimated by gear torque rate of melt mixer, respectively rate of plasticizer migration from the material during higher temperature. The plasticizer structure influence on the glass transition temperature and on the kinetics of crystallization of plasticized material was investigated by modulated differential scanning calorimetry. The behavior of material during 3D printing was also observed. Mechanical properties of printed samples, especially their elongation at break, were determined by tensile tests. The largest softening effect was observed using tributylcitrate plasticizer, where the glass temperature decreased by 35 °C and elongation at break increased by 150% compared to non-plasticized reference material. This plasticized polymeric blend showed also sufficient 3D printing properties and was used as the matrix for composites in the next part of this work. Composites were filled by kaolin, limestone, halloysit, fumed silica, talc, magnesium hydroxide and chopped flax fibers. Particle distribution in composites in dependence of used surface treatment of filler was observed by scanning electron microscopy. The influence of composite filler on rheological properties, crystallization kinetics and thermal stability of composites, was observed by viscometry and differential scanning calorimetry. Their mechanical properties and heat deflection temperature were observed on samples prepared by 3D print. Kaolin in composite material showed homogeneous particle distribution and insignificant nucleation effect and influence on thermic stability. Composite filled by kaolin also showed 18% smaller warping during 3D printing compared to non-filled reference. Consequently kaolin was evaluated as suitable inorganic filler for bioplastic composite intended for 3D print and this composite was used in the following part of this thesis. Method of mathematical prediction of Young's modulus was described for composite samples prepared by 3D print. Composites filled by one type of filler – kaolin, or limestone, resp. by combination of both fillers were investigated on the basis of the micromechanic Halpin-Tsai model modified by the semiempiric multiparametric Cerny's equation. Additive and combinational method of Young's modulus evaluation is used for composites with hybrid filling. Deflection of measured and theoretical Young's modulus value of composite filled with kaolin was decreased by established correction from 21% to 1% and for composites filled with limestone from 13% to 9%. In this manner it is possible to predict the Young's modulus of the samples prepared by 3D print.

Poly-para-xylylene films preparation and characterization of their properties

Poly-p-xylylen je základní polymer skupiny parylenů, objevený v 50. letech minulého století. V praxi se využívá několik jeho derivátů, přičemž většina je v této práci diskutována. Pro své vysoké užitné vlastnosti, a to zejména bariérové, tepelné a mechanické, je použitelný jako konzervační a ochranný povlak elektroniky, lékařských nástrojů a zařízení, nebo muzejních exponátů. Nejvýznamnější vlastností parylenu je však jeho nízká dielektrická konstanta, díky níž je i ve velmi tenkých vrstvách výborný izolant. Nanášení parylenové vrstvy na povrch substrátu se provádí nejčastěji z prekurzoru [2,2]paracyklofanu metodou chemické depozice z plynné fáze (CVD). Pro tento proces bylo navrženo a v této práci popsáno zařízení, včetně popisu jednotlivých součástí a sestavení. Předmětem této práce bylo zkoumání vlastností parylenových vrstev na vzorcích kovů. Pomocí konfokální laserové mikroskopie a optické mikroskopie v polarizovaném světle byl potvrzen výskyt četných krystalových domén, což poukazuje na vysokou krystalinitu polymeru. Měřením tloušťky vrstvy byly odhaleny a popsány nedostatky v konvenčně používaném způsobu depozice. Analytickou metodou infračervené spektroskopie (IR) byla zkoumána čistota nanesených vrstev. Metodou měření propustnosti kyslíku vrstvou parylenu naneseného na PP fólii byly vyčísleny jeho bariérové vlastnosti. Protože je velká snaha o uplatnění parylenu coby povrchové ochrany pro muzejní exponáty, byl největší význam věnován zkoušce korozní odolnosti. Zde byly navzájem porovnávány vzorky různých kovů s ochrannou vrstvou parylenu a vzorky ošetřené běžně používaným restaurátorským způsobem. Vzorky ošetřené parylenem podléhaly pouze velmi pomalé bodové korozi, naproti tomu vzorky ošetřené konvenčními pryskyřicemi byly prakticky zcela zničeny korozí.Poly-p-xylylene is a basic polymer of parylene family. It was discovered in 50s of the 20th century. In practical applications, there are used several derivates. Most of them are discussed in this thesis. Poly-p-xylylene has many utility properties, like barrier, thermal and mechanical properties. It can be used for conservation and protection of electronic equipments, medical tools and devices or museum exhibits. The most important property of parylene is its low dielectric constant which enables parylene to have good insulating properties in form of very thin layer. The most common precursor used for parylene coatings by Chemical Vapor Deposition (CVD) is [2,2]paracyclophane. Special device invented for this process was described in this thesis, including every part and assembly. The main aim of this thesis was to test properties of thin parylene layers on metal samples. High degree of polymer crystallinity was confirmed by confocal laser microscopy and optical microscopy in the polarized light measurements. Problems in the conventional method of production of parylene layers were found during the measurement of thickness of layers. Purity of deposited films was determined using Infrared spectroscopy (IR). Parylene barrier properties were quantified by the measurement of Oxygen Transmission Rate through a layer deposited on the surface of PP foil. Because the research has been mainly focused on protection of museum exhibits, the corrosion resistance test is the most important. Metal samples with thin parylene film were compared to samples with conventional restoration coating. The samples with parylene protection were slowly corroded by point corrosion. In contrast to them, the samples conserved by conventional restoration method were almost destroyed by corrosion.

PLA toughening via bamboo-inspired 3D printed structural design

Bioinspired structures can attain mechanical properties unseen in conventional artificial materials. Specifically, the introduction of a cellular structure with a precisely designed distribution of cells, cell sizes, and cell walls is expected to enhance the mechanical response. Polylactic acid (PLA) is a biodegradable polymer produced from renewable resources with very interesting properties and good three-dimensional (3D) printing processability. However, its embrittlement during ageing at room temperature after a very short period of time (a few hours) significantly reduces its usability for advanced applications. Intense effort has been invested in improving its toughness via composition modification. However, this approach can worsen some other properties, make processing more difficult, and increase the carbon footprint. Therefore, fused deposition modelling (FDM) 3D printing was used to manufacture porous bamboo-inspired structures of unmodified PLA. The toughening of PLA solely by the pore gradient, which controlled the energy dissipation mechanism, was introduced for the first time. Improvement of the ductility and work at break was observed especially for notched specimens. Prevention of catastrophic failure could enable the use of gradient porous materials in structural components. The fundamental relationships and practical hints resulting from the work provide a foundation for the future design of toughened 3D printed structures

Poly(3-hydroxybutyrate) (PHB) and Polycaprolactone (PCL) Based Blends for Tissue Engineering and Bone Medical Applications Processed by FDM 3D Printing

In the presented work, poly(3-hydroxybutyrate)-PHB-based composite blends for bone medical applications and tissue engineering are prepared and characterized. PHB used for the work was in two cases commercial and, in one case, was extracted by the chloroform-free route. PHB was then blended with poly(lactic acid) (PLA) or polycaprolactone (PCL) and plasticized by oligomeric adipate ester (Syncroflex, SN). Tricalcium phosphate (TCP) particles were used as a bioactive filler. Prepared polymer blends were processed into the form of 3D printing filaments. The samples for all the tests performed were prepared by FDM 3D printing or compression molding. Differential scanning calorimetry was conducted to evaluate the thermal properties, followed by optimization of printing temperature by temperature tower test and determination of warping coefficient. Tensile test, three-point flexural test, and compression test were performed to study the mechanical properties of materials. Optical contact angle measurement was conducted to determine the surface properties of these blends and their influence on cell adhesion. Cytotoxicity measurement of prepared blends was conducted to find out whether the prepared materials were non-cytotoxic. The best temperatures for 3D printing were 195/190, 195/175, and 195/165 degrees C for PHB-soap/PLA-SN, PHB/PCL-SN, and PHB/PCL-SN-TCP, respectively. Their mechanical properties (strengths similar to 40 MPa, moduli similar to 2.5 GPa) were comparable with human trabecular bone. The calculated surface energies of all blends were similar to 40 mN/m. Unfortunately, only two out of three materials were proven to be non-cytotoxic (both PHB/PCL blends)

Evaluation of the Properties of PHB Composite Filled with Kaolin Particles for 3D Printing Applications Using the Design of Experiment

In the presented work, poly(3-hydroxybutyrate)-PHB-based composites for 3D printing as bio-sourced and biodegradable alternatives to synthetic plastics are characterized. The PHB matrix was modified by polylactide (PLA) and plasticized by tributyl citrate. Kaolin particles were used as a filler. The mathematical method “Design of Experiment” (DoE) was used to create a matrix of samples for further evaluation. Firstly, the optimal printing temperature of the first and upper layers was determined. Secondly, the 3D printed samples were tested with regards to the warping during the 3D printing. Testing specimens were prepared using the determined optimal printing conditions to measure the tensile properties, impact strength, and heat deflection temperature (HDT) of the samples. The results describe the effect of adding individual components (PHB, PLA, plasticizer, and filler) in the prepared composite sample on the resulting material properties. Two composite samples were prepared based on the theoretical results of DoE (one with the maximum printability and one with the maximum HDT) to compare them with the real data measured. The tests of these two composite samples showed 25% lower warping and 8.9% higher HDT than was expected by the theory

Slow-Release Nitrogen Fertilizers with Biodegradable Poly(3-hydroxybutyrate) Coating: Their Effect on the Growth of Maize and the Dynamics of N Release in Soil

Fertilizers play an essential role in agriculture due to the rising food demand. However, high input fertilizer concentration and the non-controlled leaching of nutrients cause an unwanted increase in reactive, unassimilated nitrogen and induce environmental pollution. This paper investigates the preparation and properties of slow-release fertilizer with fully biodegradable poly(3-hydroxybutyrate) coating that releases nitrogen gradually and is not a pollutant for soil. Nitrogen fertilizer (calcium ammonium nitrate) was pelletized with selected filler materials (poly(3-hydroxybutyrate), struvite, dried biomass). Pellets were coated with a solution of poly(3-hydroxybutyrate) in dioxolane that formed a high-quality and thin polymer coating. Coated pellets were tested in aqueous and soil environments. Some coated pellets showed excellent resistance even after 76 days in water, where only 20% of the ammonium nitrate was released. Pot experiments in Mitscherlich vegetation vessels monitored the effect of the application of coated fertilizers on the development and growth of maize and the dynamics of N release in the soil. We found that the use of our coated fertilizers in maize nutrition is a suitable way to supply nutrients to plants concerning their needs and that the poly(3-hydroxybutyrate) that was used for the coating does not adversely affect the growth of maize plants

Production technology of dental composite

Tato bakalářská práce se zabývá vývojem a výrobou zařízení pro odtah a dělení prepregu vláknového dentálního kompozitu. Hlavním cílem byl návrh zařízení, tvorba technické dokumentace všech jeho částí, vlastní výroba a sestavení celého zařízení. Finální systém byl testován v průmyslové výrobě.This bachelor thesis deals with the development and processing of the device useful for pulling and cutting of dental fiber reinforced composite prepreg. The main goal was the designing, assembling and testing of the device and making of the technical documentation of its all components. Furthermore, the developed apparatus was implemented and tested in the industrial production.

Effect of Selected Commercial Plasticizers on Mechanical, Thermal, and Morphological Properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer Biodegradable Blends for Three-Dimensional (3D) Print

This paper explores the influence of selected commercial plasticizers structure, which are based on esters of citric acid, on mechanical and thermal properties of Poly(3-hydroxybutyrate)/Poly(lactic acid)/Plasticizer biodegradable blends. These plasticizers were first tested with respect to their miscibility with Poly(3-hydroxybutyrate)/Poly(lactic acid) (PHB/PLA) blends using a kneading machine. PHB/PLA/plasticizer blends in the weight ratio (wt %) of 60/25/15 were then prepared by single screw and corotating meshing twin screw extruders in the form of filament for further three-dimensional (3D) printing. Mechanical, thermal properties, and shape stability (warping effect) of 3D printed products can be improved just by the addition of appropriate plasticizer to polymeric blend. The goal was to create new types of eco-friendly PHB/PLA/plasticizers blends and to highly improve the poor mechanical properties of neat PHB/PLA blends (with majority of PHB) by adding appropriate plasticizer. Mechanical properties of plasticized blends were then determined by the tensile test of 3D printed test samples (dogbones), as well as filaments. Measured elongation at break rapidly enhanced from 21% for neat non-plasticized PHB/PLA blends (reference) to 328% for best plasticized blends in the form of filament, and from 5% (reference) to 187% for plasticized blends in the form of printed dogbones. The plasticizing effect on blends was confirmed by Modulated Differential Scanning Calorimetry. The study of morphology was performed by the Scanning Electron Microscopy. Significant problem of plasticized blends used to be also plasticizer migration, therefore the diffusion of plasticizers from the blends after 15 days of exposition to 110 °C in the drying oven was investigated as their measured weight loss. Almost all of the used plasticizers showed meaningful positive softening effects, but the diffusion of plasticizers at 110 °C exposition was quite extensive. The determination of the degree of disintegration of selected plasticized blend when exposed to a laboratory-scale composting environment was executed to roughly check the “biodegradability”