PLA-aPHA RESINS AND PRODUCTS

Abstract

Disclosed herein are biodegradable polymer compositions including, based on the total weight of the polymer composition, between 0.1 wt.% and 40 wt.% aPHA and between 60 wt.% and 99.9 wt.% PLA. The composition may optionally include PHA in a weight, based on the total weight of the polymer composition, between 0.1 wt.% and 35 wt.% PHA. However, when both PHA and aPHA are in the composition, the total combined weight of the PHA and aPHA based on the total weight in the polymer composition is 40 wt.% or less. The compositions may have additives included in them, such as colorants, optical brighteners, or radiation stability agents, or combinations thereof. Articles formed from the polymer compositions disclosed herein have improved mechanical properties compared to an article formed from PLA alone.

Description

Attorney Docket No. SP24-147 PLA- PHA RESINS AND PRODUCTSCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of priority under 35 U.S.C. §119 of U.S.Provisional Application Serial No.63 / 701,280 filed on September 30, 2024, the content of which is relied upon and incorporated herein by reference in its entirety. FIELD

[0002] The present disclosure relates to the field of sustainable products, and morespecifically, to resins formed from blends of polylactic acid (PLA) and amorphouspolyhydroxyalkanoate ( PHA), and to products formed from these resin blends.BACKGROUND

[0003] Most plastics used for products today are petroleum based, such as polypropyleneand polyethylene. These petroleum-based plastic products are not biodegradable and are harmful to the environment. They remain in marine and land environments, even as they break down (e.g., microplastics), and they cause pollution. Feasible, sustainable alternatives to petroleum-based plastic products are therefore needed. SUMMARY

[0004] Aspect 1. An article comprising, PHA and PLA, wherein the article is free of non-biodegradable thermoplastic polymers. The PHA is present in an amount from 0.1 wt.% to 40wt.% based on the total weight of the article, and the PLA is present in an amount from 60 wt.% to 99.9 wt.% based on the total weight of the article.

[0005] Aspect 2. The article of aspect 1, further comprising PHA, present in an amountfrom 0.1 wt.% to 39.9 wt.% based on the total weight of the article, and wherein the total amountof PHA and PHA combined is 40 wt.% or less the total weight of the article.

[0006] Aspect 3. The article of aspect 1 or aspect 2, further comprising at least one additive,present in an amount from 0.1 wt.% to 5 wt.% based on the total weight of the article.Attorney Docket No. SP24-147

[0007] Aspect 4. The article of aspect 3, wherein the at least one additive comprises oneor more of an antioxidant, a colorant, an optical brightener, a radiation stability agent, a conductive agent, a nucleating agent, and a clarifying agent.

[0008] Aspect 5. The article of any one of aspects 1-4, wherein the article has a flexuralstrength between 10,000 psi and 25,000 psi.

[0009] Aspect 6. The article of any one of aspects 1-5, wherein the article has a tensilestrain at break of between 5% and 300%.

[0010] Aspect 7. The article of any one of aspects 1-6, wherein the article has a tensilestress at break of between 2 ksi and 10 ksi.

[0011] Aspect 8. The article of any one of aspects 1-7, wherein the article has b* value foryellowing that is between 14 and -5 when the article is 1 mm in thickness.

[0012] Aspect 9. The article of any one of aspects 1-8, wherein the article has low warpageafter 24 hours in an oven at 65 °C.

[0013] Aspect 10. The article of any one of aspects 1-9, wherein the article is a tissueculture treated article.

[0014] Aspect 11. The article of any one of aspects 1-10, wherein the article has a haze of50% or less.

[0015] Aspect 12. The article of any one of aspects 1-11, wherein the article is a sterilizedarticle.

[0016] Aspect 13. The article of aspect 12, wherein the sterilized article is a high-energyirradiated article, and the high-energy irradiation is a dosage between 5 kGy and 50 kGy.

[0017] Aspect 14. The article of any one of aspects 1-13. wherein the article is a pipette, apipette tip, a cell culture plate, a tube, a tube rack, a well plate, an assay plate, a roller bottle, a liquid handling vessel, or a storage vessel.Attorney Docket No. SP24-147

[0018] Aspect 15. The article of any one of aspects 1-14, wherein the L* value for lightnessis between 65-100 when the article is 1 mm in thickness.

[0019] Aspect 16. An article comprising PHA, PLA, and a toner, wherein the article isfree of non-biodegradable thermoplastic polymers, and wherein the article has a haze of 50% orless. The PHA is present in an amount from 0.1 wt.% to 40 wt.% based on the total weight of thearticle. The PLA is present in an amount greater than 60 wt.% and less than 99.9 wt.% based on the total weight of the article.

[0020] Aspect 17. The article of aspect 16, wherein the article is a sterilized article.

[0021] Aspect 18. The article of aspect 16 or aspect 17, wherein the article is a tissueculture treated article.

[0022] Aspect 19. The article of any one of aspects 16-18, wherein the toner is a blue toner.

[0023] Aspect 20. The article of aspect 17 or 19, wherein the article has a has a b* valuethat that is at least a value of 0.2 less than the b* value of an unsterilized article having the same composition.

[0024] Aspect 21. The article of any one of aspects 16-20, wherein the article has b* valuefor yellowing that is between 6 and -5, when the article is 1 mm in thickness.

[0025] Aspect 22. The article of any one of aspects 16-21, wherein the L* value forlightness is between 65-95, when the article is 1 mm in thickness.

[0026] Aspect 23. The article of any one of aspects 16-22, wherein the article has no visualwarpage after 24 hours in an oven at 65 °C.

[0027] Aspect 24. A method of culturing cells, comprising the steps of providing an articlefor culturing cells, providing cells of a cell type to the article, and culturing the cells. The articlefor culturing cells has a composition comprising PHA and PLA, wherein the PHA is presentthe composition in an amount from 0.1 wt.% to 40 wt.% based on the total weight of the article,Attorney Docket No. SP24-147 and wherein the PLA is present in the composition in an amount from 60 wt.% to 99.9 wt.% based on the total weight of the article.

[0028] Aspect 25. The method of aspect 24, wherein the composition further comprises atleast one additive present in an amount greater than 0 wt.% and less than 5 wt.% based on the total weight of the article.

[0029] Aspect 26. The method of aspect 24 or aspect 25, wherein the article has 50% hazeor less.

[0030] Aspect 27. The method of any one of aspects 24-26, wherein the article is asterilized article, a tissue cultured treated article, or a combination thereof.

[0031] Aspect 28. The method of any one of aspects 24-27, wherein the cells of a cell typeare adherent cells.

[0032] Aspect 29. The method of any one of aspects 24-27, wherein the cells of a cell typeare cells that form three-dimensional cell cultures.

[0033] Aspect 30. The method of any one of aspects 24-27, wherein the cells of a cell typeare cells that grow in suspension.

[0034] Aspect 31. The method of any one of aspects 24-27, wherein the culturing of cellscomprises a 2D cell culture, a 3D cell culture, or a suspension culture.

[0035] Additional features and advantages will be set forth in the detailed descriptionwhich follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

[0036] It is to be understood that both the foregoing general description and the followingdetailed description are merely exemplary and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding and are incorporated in and constitute a part of this specification.Attorney Docket No. SP24-147 The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and operation of the various embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The following is a description of the figures in the accompanying drawings, givenpurely by way of non-limiting example. The figures are not necessarily to scale, and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

[0038] FIG. 1 is a one-way ANOVA graph showing the results of flexural strength testingfor articles made from with different compositions of thermoplastic polymers, including articlesmade from 100% polypropylene, 100% polystyrene, 100% PLA, and mixtures of PLA and PHA.

[0039] FIG. 2 is a one-way ANOVA graph showing the results of the tensile strain at thepoint of break testing for articles made from with different compositions of thermoplastic polymers, including articles made from 100% polypropylene, 100% polystyrene, 100% PLA, andmixtures of PLA and PHA.

[0040] FIG. 3 is a one-way ANOVA graph showing the results of tensile stress values atthe point of break testing for articles made from with different compositions of thermoplastic polymers, including articles made from 100% polypropylene, 100% polystyrene, 100% PLA, andmixtures of PLA and PHA.

[0041] FIG. 4 is a photograph that shows the amount of warpage that occurs with petridishes made from 100% polypropylene, 100% polystyrene, 100% PLA, or various mixtures ofPLA and PHA that were subjected to 65 °C for 24 hours.

[0042] FIG. 5A is a photograph of a petri dish made from 100% PLA after injectionmolding formation but before an oven test.

[0043] FIG. 5B is a photograph of the petri dish made from 100% PLA shown in FIG. 5Aafter 24 hours in a constant temperature oven at 65 °C.Attorney Docket No. SP24-147

[0044] FIG. 5C is a photograph of a petri dish made from 60% PLA, 30% Blend (a blendthat is 55% PLA and 45% PHA), and 10% PHA after injection molding formation but beforean oven test.

[0045] FIG.5D is a photograph of the petri dish made from 60% PLA, 30% Blend (a blendthat is 55% PLA and 45% PHA), and 10% PHA shown in FIG. 5C after 24 hours in a constanttemperature oven at 65 °C.

[0046] FIG. 6A is a photograph of a flat disc made from 100% PLA after injection moldingformation but before an oven test, with a trace overlay of the disc.

[0047] FIG. 6B is a photograph of a petri dish made from 70% PLA and 30% Blend (ablend that is 55% PLA and 45% PHA) after injection molding formation but before an oven test,with a trace overlay of the disc.

[0048] FIG. 6C is a photograph of the petri dish made from 100% PLA shown in FIG. 6Aafter 24 hours in a constant temperature oven at 65 °C, with a trace overlay of the disc.

[0049] FIG. 6D is a photograph of the petri dish made from 70% PLA, 30% blend (a blendof PLA and PHA that is 55% PLA and 45% PHA) shown in FIG.6B after 24 hours in a constanttemperature oven at 65 °C, with a trace overlay of the disc.

[0050] FIG. 7 is a box plot of the results of haze testing for articles made from 100%polypropylene, 100% polystyrene, 100% PLA, a mixture of 95% PLA and 5% PHA, a mixtureof 95% PLA and 5% blend (a blend of PLA and PHA that is 55% PLA and 45% PHA), amixture of 99% PLA and 1% PHA, and a mixture of 99% PLA and 1% blend.

[0051] FIG. 8 is a box plot of the results of lightness (L*) testing for articles made from100% polystyrene, 100% PLA, a mixture of 95% PLA and 5% PHA, a mixture of 94.75% PLAand 4.75% PHA and 0.5% blue toner additive (B), a mixture of 84.75% PLA and 14.75% PHAand 0.5% optical brightener additive (OB), a mixture of 84.75% PLA and 14.75% PHA and 0.5%blue toner additive (B), a mixture of 70% PLA and 30% PHA, a mixture of 69.75% PLA andAttorney Docket No. SP24-14729.75% PHA and 0.5% blue toner additive (B), and a mixture of 69.75% PLA and 29.75% PHAand 0.5% optical brightener additive (OB).

[0052] FIG. 9 is a box plot of the results of yellowness color (b*) testing for articles madefrom 100% polystyrene, 100% PLA, a mixture of 95% PLA and 5% PHA, a mixture of 94.75%PLA and 4.75% PHA and 0.5% blue toner additive (B), a mixture of 84.75% PLA and 14.75%PHA and 0.5% optical brightener additive (OB), a mixture of 84.75% PLA and 14.75% PHAand 0.5% blue toner additive (B), a mixture of 70% PLA and 30% PHA, a mixture of 69.75%PLA and 29.75% PHA and 0.5% blue toner additive (B), and a mixture of 69.75% PLA and29.75% PHA and 0.5% optical brightener additive (OB).

[0053] FIG. 10 is a box plot of the results of haze testing for articles made from 100%polystyrene, 100% PLA, a mixture of 95% PLA and 5% PHA, a mixture of 94.75% PLA and4.75% PHA and 0.5% blue toner additive (B), a mixture of 84.75% PLA and 14.75% PHA and0.5% optical brightener additive (OB), a mixture of 84.75% PLA and 14.75% PHA and 0.5%blue toner additive (B), a mixture of 70% PLA and 30% PHA, a mixture of 69.75% PLA and29.75% PHA and 0.5% blue toner additive (B), and a mixture of 69.75% PLA and 29.75% PHAand 0.5% optical brightener additive (OB).

[0054] FIG. 11A is a photograph of an article formed from a mixture of 70% PLA and30% PHA without any sterilization by gamma irradiation.

[0055] FIG. 11B is a photograph of an article formed from a mixture of 70% PLA and30% PHA after sterilization by gamma irradiation.

[0056] FIG. 11C is a photograph of an article formed from a mixture of 69.75% PLA and29.75% PHA and 0.5% blue toner without any sterilization by gamma irradiation.

[0057] FIG. 11D is a photograph of an article formed from a mixture of 69.75% PLA and29.75% PHA and 0.5% blue toner after sterilization by gamma irradiation.DETAILED DESCRIPTIONAttorney Docket No. SP24-147

[0058] The various aspects and embodiments will now be fully described herein. Theseaspects and embodiments may, however, be embodied in many different forms and should not be construed as limiting; rather, these embodiments are provided so the disclosure will be thorough and complete, and will fully convey the scope of the present subject matter to those skilled in the art. All publications, patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety.

[0059] Modifications of the disclosure will occur to those skilled in the art and to thosewho make or use the disclosure. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the disclosure, which is defined by the following claims, as interpreted according to the principles of patent law, including the doctrine of equivalents. A. Definitions

[0060] Unless defined otherwise, all terms and phrases used herein include the meaningsthat the terms and phrases have attained in the art, unless the contrary is clearly indicated or clearly apparent from the context in which the term or phrase is used. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, particular methods and materials are now described.

[0061] As used herein the terms “the,” “a,” or “an,” mean “at least one,” and should not belimited to “only one” unless explicitly indicated to the contrary. Thus, for example, reference to “a component” includes embodiments having two or more such components unless the context clearly indicates otherwise.

[0062] Unless otherwise stated, the use of individual numerical values is stated asapproximations as though the values were preceded by the word “about” or “approximately.” Similarly, the numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word “about” or “approximately.” In this manner, variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. As used herein, the terms “about” and “approximately” whenAttorney Docket No. SP24-147 referring to a numerical value shall have their plain and ordinary meanings to a person of ordinary skill in the art to which the disclosed subject matter is most closely related or the art relevant to the range or element at issue. The amount of broadening from the strict numerical boundary depends upon many factors. For example, some of the factors which may be considered include the criticality of the element and / or the effect a given amount of variation will have on the performance of the claimed subject matter, as well as other considerations known to those of skill in the art. As used herein, the use of differing amounts of significant digits for different numerical values is not meant to limit how the use of the words “about” or “approximately” will serve to broaden a particular numerical value or range. Thus, as a general matter, “about” or “approximately” broaden the numerical value. Also, the disclosure of ranges is intended as a continuous range including every value between the minimum and maximum values plus the broadening of the range afforded by the use of the term “about” or “approximately.” Consequently, recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, and each separate value is incorporated into the specification as if it were individually recited herein.

[0063] As used herein, the term “and / or,” when used in a list of two or more items, meansthat any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

[0064] As used herein, “have,” “having,” “include,” “including,” “comprise,”“comprising” or the like are used in their open ended sense, and generally mean “including, but not limited to.”

[0065] “Optional” or “optionally” means that the subsequently described element,component or circumstance may or may not occur, so that the description includes instances where the element, component, or circumstance occurs and instances where it does not.

[0066] In this document, relational terms, such as first and second, top and bottom, and thelike, are used solely to distinguish one entity or action from another entity or action, withoutAttorney Docket No. SP24-147 necessarily requiring or implying any actual such relationship or order between such entities or actions.

[0067] All scientific and technical terms used herein have meanings commonly used in theart unless otherwise specified. The definitions provided herein are to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure. B. Introduction

[0068] Petroleum-based plastic products are not biodegradable and cause significantpollution of the environment. Polylactic acid (“PLA”) is a more sustainable option than petroleum based plastic. PLA is a biodegradable aliphatic polyester that can be used in industrial composting environments. It is a thermoplastic bio-based polymer, synthesized from plant sources such as cassava roots, corn starch, sugar beet pulp, and sugar cane. The structure of the PLA molecule leads to a glass transition temperature between 55-60°C, which limits its use in applications that require higher use temperatures. The structure of the PLA molecule also allows the polymer to form crystalline phases that can increase the heat deflection temperature to 95 – 120°C. However, the crystals that are responsible for this elevated heat deflection temperature also scatter light leading to parts that are opaque. This limits its use to non-transparent applications.

[0069] Polyhydroxyalkanoate (“PHA”) is also a biodegradable aliphatic polyester,produced by the polymerization of monomers in the family of hyroxyalkanoates. Prokaryotic microorganisms, including bacteria and archaea produce PHA as an energy storage molecule and have enzymes to depolymerize PHA for use. Because of this, PHA is easily biodegraded by these microorganisms in soil or water. Varying the monomer makeup of PHA can lead to polymers that are flexible or elastic, allowing for significant variation in the mechanical properties of the polymer.

[0070] Additional features and advantages will be set forth in the detailed descriptionwhich follows and will be apparent to those skilled in the art from the description or recognized by practicing the embodiments as described in the following description, together with the claims and appended drawings.Attorney Docket No. SP24-147 C. Polymeric Compositions

[0071] According to aspects of the present disclosure, it has been found that polymericcompositions that include both PLA and PHA form polymeric parts (articles) that arebiodegradable, have sufficient transparency, and not overly brittle. The polymer compositions ofthe present disclosure comprise the biodegradable thermoplastic polymers PLA and PHA, andoptionally, PHA. The PLA may comprise one or more stereoisomers of PLA, such as poly-L-lactide (“PLLA”), poly-D-lactide (“PDLA”), or a combination thereof (“PDLLA”). The PHAmay comprise at least 30% mole fraction of 4-hydroxybutyrate (“4HB”) in a PHA copolymer poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (“P3HB4HB”).

[0072] Regarding PHA, embodiments of the polymer compositions described herein maycomprise, based on a total weight of the polymer composition, from 0.1 wt.% to 40 wt.% PHA.For example, without limitation, the polymer compositions may comprise PHA in an amount,based on the total weight of the polymer composition, from 0.1 wt.% to 35 wt.%, from 0.1 wt.% to 30 wt.%, from 0.1 wt.% to 25 wt.%, from 0.1 wt.% to 20 wt.%, from 0.1 wt.% to 15 wt.%, from 0.1 wt.% to 10 wt.%, from 0.1 wt.% to 5 wt.%, from 1 wt.% to 40 wt.%, from 5 wt.% to 40 wt.%, from 10 wt.% to 40 wt.%, from 15 wt.% to 40 wt.%, from 20 wt.% to 40 wt.%, from 25 wt.% to 40 wt.%, from 30 wt.% to 40 wt.%, or from 35 wt.% to 40 wt.%, or at any value or range between0.1 wt.% and 40 wt.%. In one embodiment, the polymer composition may comprise PHA in anamount from 1 wt.% to 30% wt.%, based on a total weight of the polymer composition. In anotherembodiment, polymer compositions may comprise PHA in an amount from 5 wt.% to 30 wt.%,based on a total weight of the polymer composition. In yet another embodiment, polymercompositions may comprise PHA in an amount from 0.3 wt.% to 25 wt.%

[0073] Regarding PLA, embodiments of the polymer compositions described herein maycomprise, based on a total weight of the polymer composition, from 55 wt.% to 99.9 wt.% PLA.For example, without limitation, the polymer compositions may comprise PHA in an amount,based on the total weight of the polymer composition, from 60 wt.% to 99.9 wt.%, from 65 wt.% to 99.9 wt.%, from 70 wt.% to 99.9 wt.%, from 75 wt.% to 99.9 wt.%, from 80 wt.% to 99.9 wt.%, from 85 wt.% to 99.9 wt.%, from 90 wt.% to 99.9 wt.%, from 95 wt.% to 99.9 wt.%, from 60 wt.%Attorney Docket No. SP24-147 to 95 wt.%, from 60 wt.% to 90 wt.%, from 60 wt.% to 85 wt.%, from 60 wt.% to 80 wt.%, from 60 wt.% to 75 wt.%, from 60 wt.% to 70 wt.%, or from 60 wt.% to 65 wt.%, or at any value or range between 55 wt.% and 99.9 wt.%. In one embodiment, the polymer composition comprises PLA in an amount from 65 wt.% to 99 wt.%, based on a total weight of the polymer composition. In another embodiment, the polymer composition comprises PLA in an amount from 65 wt.% to 95 wt.%, based on a total weight of the polymer composition.

[0074] The PLA may be PLLA, PDLA, or a combination thereof. In some embodiments,the composition of the PLA is 100 wt.% PLLA based on the total weight of PLA in the polymer composition. In some embodiments, the composition of the PLA is 100 wt.% PDLA based on the total weight of PLA in the polymer composition. In some embodiments, the composition of the PLA is a blend of PDLA and PLLA. In one embodiment, the composition of the PLA is bewteen about 99 wt.% and 100 wt.% PLLA, with the difference PDLA (i.e., 100 wt.% minus the PLLA wt.%), based on the total weight of PLA in the polymer composition. In another embodiment, the composition of the PLA is from 95 wt.% to 100 wt.% PLLA, with the difference PDLA (i.e., 100 wt.% minus the PLLA wt.%), based on the total weight of PLA in the polymer composition.

[0075] In some embodiments, in addition to PLA and PHA, the polymer compositionmay further comprise non-amorphous PHA (i.e., “PHA”). In these embodiments, the polymer composition may comprise, based on the total weight of the polymer composition, from more than 0 wt.% to 39.9 wt.% of PHA. For example, the polymer composition may comprise PHA in an amount from 0.1 wt.% to 39.9 wt.%, from 1.0 wt.% to 39.9 wt.%, from 5.0 wt.% to 39.9 wt.%, from 10.0 wt.% to 39.9 wt.%, from 15.0 wt.% to 39.9 wt.%, from 20.0 wt.% to 39.9 wt.%, from 25.0 wt.% to 39.9 wt.%, from 30.0 wt.% to 39.9 wt.%, from 35.0 wt.% to 39.9 wt.%, from 0.1 wt.% to 30.0 wt.%, from 0.1 wt.% to 25.0 wt.%, from 0.1 wt.% to 20.0 wt.%, from 0.1 wt.% to 15.0 wt.%, from 0.1 wt.% to 10.0 wt.%, or from 0.1 wt.% to 5.0 wt.%, or any value or range that is from more than 0 wt.% to 39.9 wt.%. In some embodiments, the polymer composition may be free of PHA. In one specific embodiment, the polymer composition comprises between about 0.1 wt.% and about 25 wt.% PHA. In another specific embodiment, the polymer composition comprises between about 0.5 wt.% and about 20 wt.% PHA.Attorney Docket No. SP24-147

[0076] However, in embodiments where the polymer composition comprises both PHAand PHA, the total weight of the combination of PHA and PHA based on the total weight ofthe polymer composition is 40 wt.% or less. For example, a polymer composition comprising bothPHA and PHA may have 25 wt.% PHA and 15 wt.% PHA, 15 wt.% PHA and 20 wt.% PHA,5 wt.% PHA and 12 wt.% PHA, or 17 wt.% PHA and 8 wt.% PHA, based on the total weightof the polymer composition. In another example, a polymer composition comprising both PHAand PHA may have between 0.1 wt.% and 39.9 wt.% PHA, and between 0.1 wt.% and 39.9wt.% PHA, based on the total weight of the polymer composition such that the combination totals 40 wt.% of the composition or less. However, these are merely exemplary any combination ofwt.% of PHA and PHA may be used that has a combined total weight in the polymer compositionof 40 wt.% or less.

[0077] In some embodiments, the polymer composition may further comprise one or moreadditives. The additives that may be included in the polymer composition are not necessarily limited. Additives and additive packages for polymer compositions are available through commercial vendors. In embodiments, the additives may comprise radical scavengers clarifying agents, optical brighteners, nucleating agents, antistatic agents, colorants, radiation stability agents or packages, and / or conductive agents. Radical scavengers may be included in the polymer composition to prevent degradation of the polymers. Clarifying agents and / or nucleating agents may improve the clarity of articles formed from the polymer composition. Increasing the number of relatively small crystalline structures in the article may reduce the light scattered by the crystalline phases improving the clarity of articles formed from the polymer composition. Antistatic agents may reduce the resistivity of the polymer composition to provide static protection. Optical brighteners can absorb ultraviolet (UV) light and reemit it. Colorants may be included in the polymer composition to impart color to articles formed form the polymer composition. Suitable colorants may be selected for use in transparent, translucent, or opaque articles, including toners, such as a blue toner. Radiation stability agents or packages may be included in the polymer composition to reduce the effects of irradiation on the polymer composition, including polymer degradation, and they may include ingredients such as antioxidants. Conductive agents may be included in the polymer composition to improve the electrical conductivity of the polymer composition. Conductive agents may include, for example,Attorney Docket No. SP24-147 carbon black and carbon fibers. Some conductive agents, such as carbon black, may also impart color to the polymer composition and articles formed from the polymer composition.

[0078] In embodiments where the polymer composition further comprises one or moreadditives, the polymer composition may comprise, based on the total weight of the polymer composition, from more than 0 wt.% to 5 wt.% of the one or more additives. For example, the polymer composition may comprise the one or more additives in an amount from 1 wt.% to 5 wt.%, from 0.5 wt.% to 5 wt.%, from 1 wt.% to 5 wt.%, from 1.5 wt.% to 5 wt.%, from 2 wt.% to 5 wt.%, from 2.5 wt.% to 5 wt.%, from 3 wt.% to 5 wt.%, from 3.5 wt.% to 5 wt.%, from 4 wt.% to 5 wt.%, from 4.5 wt.% to 5 wt.%, from more than 0 wt.% to 4.5 wt.%, from more than 0 wt.% to 4 wt.%, from more than 0 wt.% to 3.5 wt.%, from more than 0 wt.% to 3 wt.%, from more than 0 wt.% to 2.5 wt.%, from more than 0 wt.% to 2 wt.%, from more than 0 wt.% to 1.5 wt.%, from more than 0 wt.% to 1 wt.%, from more than 0 wt.% to 0.5 wt.%, or any value or range that is from more than 0 wt.% to 5 wt.%. In some embodiments, the polymer composition may be free of additives.

[0079] The polymeric compositions of the present disclosure can be used to formpolymeric parts (articles) that have improved mechanical properties (such as flexural strength and tensile stress / strain), improved transparency, and improved heat deflection temperatures than other currently available biodegradable thermoplastic polymers. The polymeric compositions assist in forming the polymeric parts by decreasing shear and improving formation of polymeric parts at temperatures over 55 °C. Polymeric parts formed from the polymeric compositions described herein will now be described. D. Articles Formed from the Polymeric Compositions

[0080] Embodiments of the polymer compositions described herein may be used to formvarious articles. Such articles may comprise the polymer compositions described in the previous section. In some embodiments, the articles may be formed from the polymer compositions. In some embodiments, the articles may consist essentially of the polymer composition.

[0081] The polymeric parts (articles) formed from polymeric compositions of the presentdisclosure have increased toughness, flexural strength, and heat deflection compared to 100 wt.%Attorney Docket No. SP24-147 PLA. The articles comprising the polymer composition are not necessarily limited. For example, they may have various applications for biological matter. In one or more embodiments, an article may comprise a pipette tip, a pipette (e.g., serological pipettes and other transfer pipettes), a tube (e.g. centrifuge tubes, liquid handling tubes, or other tube types), a tube rack, a storage vessel, a plate for cell culture (e.g., agar plates, adherent cell culture plates), well plates (e.g., well plates for two-dimensional or three-dimensional cell cultures, and well plates for assays), an assay plate (e.g., PCR plates), a liquid handling vessel, a liquid storage vessel, a packaging container, or a laboratory consumable, among other examples. As described herein, a “laboratory consumable” refers to any item for laboratory use that is replaced regularly after it is used or after it wears down. In some embodiments, the article comprises a pipette tip, a tube (including polymeric chain reaction tubes, centrifugation tubes, etc.), a pipette rack, a pipette, a cell culture plate, a well plate (such as a 1-well, 2-well, 6-well, 12-well, 24-well, 48-well, 96-well, 384-well, or 1536-well plate), a deep-well plate (i.e., a storage block), an assay plate, a storage vessel, a rack or crate for tubes or plates, or a flask.

[0082] Flexural strength refers to the ability of a polymeric part to resist deformation undera given load. Measurements of a polymeric part’s flexural strength are tested under a standardized test, ASTM D790. The flexural strength of polymeric parts formed from polymeric compositions of the present disclosure is at value from 6,000 psi to 25,000 psi, or at any value or in any range therebetween. In some embodiments, the flexural strength is at a value from 6,000 psi to 24,000 psi, from 6,000 psi to 23,000 psi, from 6,000 psi to 22,000 psi, from 6,000 psi to 21,000 psi, from 6,000 psi to 20,000 psi, from 6,000 psi to 19,000 psi, from 6,000 psi to 18,000 psi, from 6,000 psi to 17,000 psi, from 6,000 psi to 16,000 psi, from 6,000 psi to 15,000 psi, from 6,000 psi to 14,000 psi, from 6,000 psi to 13,000 psi, from 6,000 psi to 12,000 psi, from 6,000 psi to 11,000 psi, from 6,000 psi to 10,000 psi, from 7,000 psi to 13,000 psi, from 8,000 psi to 16,000 psi, from 9,000 psi to 19,000 psi, from 10,000 psi to 25,000 psi, from 11,000 psi to 25,000 psi, from 11,000 psi to 24,000 psi, from 11,000 psi to 23,000 psi, from 11,000 psi to 22,000 psi, or from 11,000 psi to 21,000 psi. In one specific embodiment, the flexural strength is at a value from 11,000 psi to 21,000 psi. In another specific embodiment, the flexural strength is at a value from 16,000 psi to 25,000 psi. In another specific embodiment, the flexural strength is at a value from 11,000 psi to 16,000 psi.Attorney Docket No. SP24-147

[0083] Tensile strain is the percentage increase in length that can occur in an article formedfrom the polymeric compositions described herein before a given amount of tension causes the article to break. Measurements of a polymeric part’s tensile strain is also measured under a standardized test, ASTM D638. The tensile strain at break of polymeric parts formed from polymeric compositions of the present disclosure is at a value from 5% to 300%, or at any value or in any range therebetween. In some embodiments, the tensile strain at break is at a value from 5% to 275%, from 5% to 250%, from 5% to 225%, from 5% to 200%, from 5% to 175%, from 5% to 150%, 5% to 125%, from 5% to 100%, from 5% to 75%, from 5% to 50%, from 5% to 25%, from 5% to 20%, from 5% to 15%, or from 5% to 10%. In one specific embodiment, the tensile strain at break is at a value from 5% to 50%.

[0084] Tensile strength refers to the ability of an article formed from the polymericcompositions to resist breaking under tensile stress. It is measured as the force per unit area on the article that is needed to break the article. The test for tensile strength is standardized in ASTM D638. The tensile stress at break of polymeric parts formed from polymeric compositions of the present disclosure is at a value from 1 ksi to 10 ksi, or at any value or in any range therebetween. In some embodiments, the tensile stress at break is from 2.5 ksi to 10 ksi, from 3.0 ksi to 10 ksi, from 3.5 ksi to 10 ksi, from 4.0 ksi to 10 ksi, from 4.5 ksi to 10 ksi, from 5.0 ksi to 10 ksi, from 5.5 ksi to 10 ksi, from 6.0 ksi to 10 ksi, from 6.5 ksi to 10 ksi, from 7.0 ksi to 10 ksi, from 7.5 ksi to 10 ksi, or from 8.0 ksi to 10 ksi. In one specific embodiment, the tensile strength at break is between 5 psi and 10 ksi. In another specific embodiment, the tensile strength at break is between 1 ksi and 5 ksi.

[0085] In some embodiments, polymeric parts formed from the polymeric compositionsdescribed herein have low warpage. Warpage is a phenomenon, observed as curling or other distortions with the form of the polymeric part, that becomes present when polymeric parts are exposed to extended periods of heat. Warpage is tested for by subjecting a polymeric part to heat in an oven at temperature of 65 °C for 24 hours. The test for warpage is run by heating an oven to 65 °C, placing weigh boats upside down on the racks in the oven, placing polymeric parts formed from a composition onto the upside down weigh boat, heating the polymeric parts at 65 °C for 24 hours, removing the polymeric parts from the oven, then looking for any changes to the concavity or convexity of the polymeric parts with visual observation as compared to a polymeric part havingAttorney Docket No. SP24-147 the same composition that had not been heated. The term “low warpage” refers to no visible changes to the concavity or convexity of a polymeric part (article) when viewed by visual observation.

[0086] The yellowness (b*) of an article is a property that can be measured for articlesformed from compositions of the present disclosure. As described herein, yellowness (b*) may be measured according to ASTM D2244. For an article formed from the compositions described herein, the yellowness (b*) of the article may have a b* value that is between -5 to 14, or in any rage or at any value therebetween. In some embodiments, the yellowness (b*) of the article may have a b* value that is between -5 to 13, -5 to 12, -5 to 11, -5 to 10, -5 to 9, -5 to 8, -5 to 7, -5 to 6, -5 to 5, -5 to 4, -5 to 3, -5 to 2, -5 to 1, -5 to 0, -4 to 14, -3 to 14, -2 to 14, -1 to 14, 0 to 14, 1 to 14, 2 to 14, 3 to 14, 4 to 14, 5 to 14, 6 to 14, 7 to 14, 8 to 14, 9 to 14, 10 to 14, -5 to 10, -5 to 5, -4 to 9, -3 to 8, -2 to 6, 0 to 6, or in any range or at any value between any of these ranges. In some embodiments, the article has a b* value in any of the foregoing ranges (or at particular value in those ranges) when the article has a thickness of 1 mm.

[0087] The lightness (L*) of an article is also a property that can be measured for articlesformed from compositions of the present disclosure. As described herein, lightness (L*) may also be measured according to ASTM D2244. For an article formed the compositions described herein, the lightness (L*) of the article may have a L* value of between 65 and 100. In some embodiments, the lightness (L*) of the article may have a L* value of between 65 and 100, between 70 and 100, between 75 and 100, between 80 and 100, between 85 and 100, or the lightness (L*) may be in any other range or at any value between 65 and 100. In one embodiment, the lightness (L*) of the article may have a L* value between 70 and 95. In some embodiments, the article has a L* value in any of the foregoing ranges (or at particular value in those ranges) when the article has a thickness of 1 mm.

[0088] Haze is a phenomenon that occurs when light scatters as it passes through apolymeric part (article). The higher the haze, the milkier the polymeric part appears. Haze can be measured using ASTM D1003 (method B using an integrating sphere spectrophotometer). In some embodiments, polymeric parts formed from the polymeric compositions described herein have a haze of 50% or less. In some embodiments, the haze of the polymeric parts is from 0% to 45%,Attorney Docket No. SP24-147 from 0% to 40%, from 0% to 35%, from 0% to 30%, from 0% to 25%, from 0% to 20%, from 0% to 15%, from 0% to 10%, from 5% to 50%, from 10% to 50%, from 15% to 50%, from 20% to 50%, from 25% to 50%, from 30% to 50%, from 35% to 50%, from 40% to 50%, from 5% to 25%, or at any value or range between 0% and 50%.

[0089] In some embodiments, an article formed from a polymeric composition asdescribed herein is sterilized with a dosage of high-energy irradiation (gamma, x-ray, or e-beam) that is greater than or equal to 5 kGy and less than or equal to 50 kGy dosage, or at any range or value therebetween. In one embodiment, an article formed from a polymeric composition as described herein is sterilized with a dosage of high-energy irradiation (gamma, x-ray, or e-beam) greater than or equal to 15 kGy and less than or equal to 30 kGy, or at any range or value therebetween. In one specific embodiment, an article formed from a polymeric composition as described herein is sterilized with a dosage of gamma irradiation of about 20 kGy.

[0090] Unexpectedly, it has been found that compositions of the present disclosure thatinclude certain additives improve the yellowing (b*) of articles formed from those compositions after sterilization with high energy irradiation, as compared to the same composition that is not irradiated. An optical brightener is one additive that unexpectedly improves the yellowing of the article upon sterilization. In some embodiments, a high-energy irradiation sterilized article formed from a composition of the present disclosure comprising an additive that is an optical brightener has a lower yellowing (b*) value than an unsterilized article having the same composition. In one embodiment, a sterilized article formed from a composition of the present disclosure comprising an additive that is an optical brightener has a b* value that that is at least a value of 0.2 less than the b* value of an unsterilized article having the same composition. In another embodiment, a sterilized article formed from a composition of the present disclosure comprising an additive that is an optical brightener has a b* value that that is at least a value of 0.5 less than the b* value of an unsterilized article having the same composition. In some embodiments, a sterilized article formed from a composition of the present disclosure comprising an additive that is an optical brightener has a b* value that is between a b* value of 0.2 and 5 less than the b* value of an unsterilized article having the same composition. In other embodiments, a sterilized article formed from a composition of the present disclosure comprising an additive that is an optical brightener has a b* value that is between 0.5 and 5, between 1 and 5, between 2 and 5, between 3 and 5, orAttorney Docket No. SP24-147 between 4 and 5, less than the b* value of an unsterilized article having the same composition. In some embodiments, the article has a b* value in any of the foregoing ranges (or at particular value in those ranges) when the article has a thickness of 1 mm.

[0091] A blue toner (a type of colorant additive) is another additive that unexpectedlyimproves the yellowing of the article upon sterilization. In some embodiments, a high-energy irradiation sterilized article formed from a composition of the present disclosure comprising an additive that is a blue toner has a lower (b*) value than an unsterilized article having the same composition. In one embodiment, a sterilized article formed from a composition of the present disclosure comprising an additive that is a blue toner has a b* value that that is at least a value of 0.2 less than the b* value of an unsterilized article having the same composition. In another embodiment, a sterilized article formed from a composition of the present disclosure comprising an additive that is a blue toner has a b* value that that is at least a value of 0.5 less than the b* value of an unsterilized article having the same composition. In some embodiments, a sterilized article formed from a composition of the present disclosure comprising an additive that is a blue toner has a b* value that is between a b* value of 0.2 and 5 less than the b* value of an unsterilized article having the same composition. In other embodiments, a sterilized article formed from a composition of the present disclosure comprising an additive that is a blue toner has a b* value that is between 0.5 and 5, between 1 and 5, between 2 and 5, between 3 and 5, or between 4 and 5, less than the b* value of an unsterilized article having the same composition. In some embodiments, the article has a b* value in any of the foregoing ranges (or at particular value in those ranges) when the article has a thickness of 1 mm.

[0092] A surface of the article may be a substrate for adherent cells to attach to (a tissueculture treated surface). Such surfaces are commonly used for 2D cell cultures. In some embodiments, cells attach directly to the surface of the article without any modifications to the surface. In some embodiments, the surface of the article is modified to improve cell adherence. Any tissue culture treatment known to those of ordinary skill in the art may be used.

[0093] In some embodiments, the surface of the article is tissue cultured treated byrendering the surface with cell adhesive properties through physical treatment of various types of plasmas, process gases, and / or chemicals known in the industry, including for example, vacuum-Attorney Docket No. SP24-147 gas plasma treatment and corona-gas or corona discharge treatment. In other embodiments, the surface of the article may be tissue culture treated by chemically treating the surface to improve cell adherence, including by treatments with poly-D-lysine, among others known to those of skill in the art. In other embodiments, the surface of the article may be tissue culture treated by grafting cell adhesion molecules onto the interior surface. Grafting of cell adhesion molecules may be done by any method known to those of skill in the art, such as adsorption of extracellular matrix proteins or mimetics onto the surface. Examples of cell adhesion molecules for grafting include cell adhesion peptides from cell adhesion proteins such as collagen, laminin, fibronectin, vitronectin, and others known to those of ordinary skill in the art. In yet other embodiments, the surface of the article may be tissue culture treated by coating the surface with a material that improves cell adhesion. For example, the surface of the article can be coated with a thin layer of a biocompatible hydrogel, such as collagen or other extracellular matrices (e.g., Corning®Matrigel®, Corning®Synthemax®-I, and Corning®Sythemax®-II), among other known to those of ordinary skill in the art.

[0094] A surface of the article may instead be an ultra-low attachment (ULA) surface thatresists cell adherence. Such surfaces are commonly used with 3D cell cultures. In some embodiments, cells resist attaching directly to the surface of the article without any modifications to the surface. In some embodiments, the surface of the article is modified to increase the resistance of cell adherence. Any ULA treatment known to those of ordinary skill in the art may be used. In some embodiments, the ULA treatment includes coating a layer of a hydrophilic, neutrally charged coating onto the surface of the article. The coating may comprise neutrally charged and / or hydrophilic molecules or proteins, or a combination thereof.

[0095] In one aspect of the disclosure, an article comprises, based on a total weight of thearticle, 0.1 wt.% to 40 wt.% PHA and 60 wt.% to 99.9 wt.% PLA and the article is free of non-biodegradable thermoplastic polymers. The article has 50% haze or less, as measured by UV / VIS spectroscopy with the protocols in ASTM D1003 (method B using an integrating sphere spectrophotometer). The article may further comprise, based on total weight of the article, greater than 0 wt.% and less than or equal to 5 wt.% of an additive selected from a colorant or an optical brightener, and the colorant is a toner. The toner may be a blue toner. The article may further have a lightness (L*) value of between 65 and 100, as measured by UV / VIS spectroscopy with theAttorney Docket No. SP24-147 protocols in ASTM 2244, using a 1 mm thick article. The article may further have a yellowness (b*) value that is between -5 and 14, as measured by UV / VIS spectroscopy with the protocols in ASTM 2244, using a 1 mm thick article.

[0096] In another aspect, an article comprises, based on a total weight of the article, 0.1wt.% to 40 wt.% PHA and 60 wt.% to 99.9 wt.% PLA and the article is free of non-biodegradablethermoplastic polymers. The article has 50% haze or less, as measured by UV / VIS spectroscopy with the protocols in ASTM D1003 (method B using an integrating sphere spectrophotometer). The article has a flexural strength of between 10,000 psi and 25,000 psi, a tensile strain at break of between 5% and 300%, and a tensile stress at break of between 2 ksi and 10 ksi.

[0097] With either of these aspects, the article may have no visual warpage (low warpage)after 24 hours in an oven at 65 °C. Likewise, with either of these aspects, the article may be a sterilized article. And likewise, with either of these aspects, the article may be tissue culture treated or may be ultra-low attachment treated.

[0098] Methods to Culture Cells in Formed Articles

[0099] When an article comprising a composition of the present disclosure is formed intoan article for culturing cells (including but not limited to a petri dish, a multi-well plate, and a roller bottle), cells of a cell type may be cultured in the article. It should be understood that any type of formed article that can be used for culturing cells that comprises the compositions described herein may be used as the article for culturing cells. Cells that may be used for culturing cells may be any adherent or non-adherent cell type for 2D cell culture, 3D cell culture, suspension culture, or any other culture types (e.g., microchip cultures) known to those of ordinary skill in the art.

[0100] In some embodiments, an article comprising a composition described herein is forculturing 2D cell culture and is a tissue culture treated article. The article may be sterilized or unsterilized. In other embodiments, an article comprising a composition described herein is for culturing 3D cell culture and is an ultra-low attachment treated article. The article may be sterilized or unsterilized. In yet other embodiments, an article comprising a composition described herein is for culturing cells in suspension and is an untreated article (i.e., does not have a surface treatment to affect cell adhesion). The article may be sterilized or unsterilized. However, these embodimentsAttorney Docket No. SP24-147 are exemplary only and any of the articles for culturing 2D cell culture, 3D cell culture, suspension cell cultures, or any other culture types known to those of ordinary skill in the art, may be untreated, tissue culture treated, ultra-low attachment treated, or have other surface treatments.

[0101] A method for culturing cells includes the steps of providing an article comprisingone of the compositions described herein, providing cells of a cell type to the article, and culturing the cells. The culturing of cells is known to those of ordinary skill in the art and typically includes providing a cell growth media and then allowing the cells to proliferate (expand) for a desired amount of time before harvesting the cells from the media. The culturing of cells may comprise a 2D cell culture, a 3D cell culture, a suspension culture, or other types of cultures known to those of ordinary skill in the art. In some embodiments, the culturing of cells comprises a 2D cell culture. In other embodiments, the culturing of cells comprises a 3D cell culture. In yet other embodiments, the culturing of cells comprises a suspension culture. E. Methods to Form Articles

[0102] Methods for forming polymeric parts (articles) comprising the polymercompositions disclosed herein are not necessarily limited. In some embodiments, articles comprising the polymer composition may be formed by injection molding, blow molding, extrusion, compression molding, or any other suitable processes. In some embodiments, methods for forming an article comprising the polymer composition may comprise solidifying a polymer composition within a mold to form an article comprising the polymer composition and removing the article from the mold.

[0103] In one or more embodiments, the polymer composition may be disposed into themold. In such embodiments, the polymer composition is formed outside the mold and before it isdisposed into the mold. The polymer composition may be formed by mixing the PHA, PLA, andoptionally, PHA and / or one or more additives, each of which are previously described. The polymer composition may then be disposed into the mold and solidified within the mold to form an article comprising the polymer composition.Attorney Docket No. SP24-147

[0104] While the present disclosure includes a limited number of embodiments, thoseskilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the present disclosure. EXAMPLES

[0105] The embodiments described herein will be further clarified by the followingexamples. Example 1

[0106] Polymer compositions comprising standard thermoplastic polymers and varyingamounts of PHA and PHA were formed by blending the ingredients described in Table 1 in thecomposition amounts described in Table 2. The compositions of Table 2 are given in wt.%.

[0107] Table 1Attorney Docket No. SP24-147

[0108] Table 2Attorney Docket No. SP24-1471“Blend” as used in this Table and the rest of the Examples, is a pre-combined mixture of PLAand PHA comprising 55% PLA and 45% PHA.Example 2

[0109] The compositions from Table 2 were formed into articles (flat pieces or petri dishes)and then tested for flexural strength, tensile strain at break, tensile stress at break, warpage, and haze. Each of the analyses are separately described below. Flexural Strength

[0110] The flexural strength of articles formed by injection molding into flat pieces calledflex bars sized for use with ASTM D790 from the polymeric compositions of Table 2 was investigated. For each flex bar, ASTM D790 protocols were followed to generate flexural strength results. A total of ten flex bars were tested for each composition listed in Table 2. The results of the flexural strength tests are summarized in Table 3 below and are graphically shown in FIG.1.

[0111] Table 3Attorney D .tS.gvA ts eT9tseT8tseT7tse )iTsp(h6ttsgenTert5S tlsaerTuxelF4tseT3tseT3 7 3 92t 6e53573 0 3 12 6 7 s11 4 2 0 5 132820033641784930998 6 T 1 2 1 1 1 1 1 2 19 2 4 3 9 6 6 1 81 2 00 53 2 4 4 7 2 5 2 7ts 4 5 8 0 9 7 4 9 68 4e8 68 9 2 6 0 9 9 9 9T 1 1 1 1 1 1 1 1 1A HsAn PA Ad d dn n n1 2r oA0iHe 1H H:tS e e e0 0l l l P P PP PiPL : 5 5 1 1sd: : : :mP P 03 3P : :nB B B: : :0y o: :l5 5 9 90 03::p 0e 0 09 9 9 9l 7 70A A AA AoA0 0100P 1 1 6Bm1 :L L LoL LLP P P P P PA C LPAttorney Docket No. SP24-147

[0112] Flexural strength values were lowest for flex bars formed from compositions having100% PP1 and 100% PP2. Flex bars formed from compositions having 100% PLA, 99% PLA:1% Blend had the highest flexural strength values, with flex bars formed from compositions having5% PHA or less being the next highest values. The flex bars having a composition with 100%PS had lower flexural strength values than the flex bars from 100% PLA and those havingcompositions with 5% PHA or less, but higher than those with 100% polypropylene and thosewith higher amounts of PHA (70% PLA:30% PHA; 60% PLA:30% Blend:10% PHA; 70%PLA:30% Blend). Tensile Strain at Break

[0113] The tensile strain (extension) at break of articles formed by injection molding flatpieces resembling dumbbells for use with ASTM D638 from the polymeric compositions of Table 2 was investigated. For each dumbbell, ASTM D638 protocols for tensile strain were followed to generate the tensile strain results. A total of ten dumbbells were tested for each composition in Table 2. The results of the tensile strain tests are summarized in Table 4 below and are graphically shown in FIG. 2.

[0114] Table 4Attorney Doc . . tS.gvA tseT 9tseT8tseT) % (7k tsaeer TBta6t)sneoTisne5txtsE(eTnia4rttsSeeTlis3neTtse4504.6.T74611129221.91128.8.8.51. 0 6 8 3ts7 43.62. 9.31 .0.80.0.eT 5 5 8 751 1 1 13112.5 0 1 1 7 2 7. . . . . . .4 4 5ts. . .5 47 86 0 4 290 3e6 4 8 3 7 1 1 1 TA Hsn PA A Ad d dn n n1 2r oA0ie 1H H H:tS e e e0 0l l l P P PP PiPL : 5 5 1 1sd: : : :mP P 03 3P : :nB B B: : :0y o: : :l5 5 9 930 0 :p 0e 0 09 9 9 9l 7 70A A AA A Ao10 0 00P 1 1 6Bm1 :L L LoL L LP P P P P PA C LPAttorney Docket No. SP24-147

[0115] The dumbbells formed from compositions comprising 100% PLA and 100% PShad the lowest tensile strains at break, with dumbbells formed from compositions comprising 5% PHA or less having only slightly higher tensile strains at break. The dumbbells formed from compositions having 100% PP1 or 100% PP2 had higher tensile strain at break values than dumbbells formed from 100% PLA, 100% PS, and the dumbbells formed from compositionscomprising 5% PHA or less. Dumbbells formed from compositions comprising higher amountsof PHA (70% PLA:30% Blend; 60% PLA:30% Blend:10% PHA; and 70% PLA:30% PHA)had the highest tensile strain extensions at break of the compositions tested. Tensile stress at Break

[0116] The tensile stress at break was investigated for the dumbbell shaped articles madefor the tensile elongation tests above. For each article, ASTM D638 protocols for tensile stress were followed to generate the tensile stress results. The results of the tensile stress tests are summarized in Table 5 below and are illustrated in FIG.3.

[0117] Table 5Attorney Dock . . tSveD.gvA tse01T 9tseT8tseT7ts)iseTk ( ka6tesreBTtas5s tesrteTSeli4tssneeTT3tseT2ts0.9.4.2.0.1.7. 0.6.8 30 0. .032 3 7 8 1 4 1e1 1 1 1 T17 2 7. . .4 1 4 4 1 4 4 5ts. . . . . . . .2 4 7 8 1 0 1290 3e1 1 1 TA Hsn PA A Ad d dn n n1 2r oA0ie 1H H H:tS e e e0l0l l P P PP PPi L : 5 5 1 1sd: : : :mP P 03 3P : :nB B B: : :0ylo: : :5 5 9 90 03:p 0e 0 09 9 9 9l07 7A A AoA A A10 0 00P 1 1 6Bm1 :L L LoL L LP P P P P PA C LPAttorney Docket No. SP24-147

[0118] Dumbbells formed from the composition having 100% PLA had the highest tensilestrength at break, while dumbbells formed from the compositions comprising the higher amounts of the amorphous PHA had the lowest tensile strength at break. The dumbbell formed from the composition having 100% PS had a high tensile strength at break, but not as high as the dumbbell formed from the composition with 100% PLA. The dumbbells formed from the two 100% polypropylene compositions had lower tensile strength at break that the dumbbells formed fromthe 100% PLA, 100% PS, and compositions comprising 5% PHA or less.Warpage The warpage of articles formed from certain polymeric compositions described below was investigated. The articles for these compositions were formed into either 3.2 mm thick discs having a 63 mm diameter or petri dishes that were 1 mm thick with a 35 mm internal diameter were investigated. For each type of article, a constant temperature oven was preheated to 65 °C. Weigh boats were placed upside down on oven racks inside the oven. The discs and petri dishes were placed on the weigh boats and the sample were left in the oven for 24 hours before they were removed and visually observed for any changes to shape. The results of the warpage tests are shown in FIGS.4-6.

[0119] FIG. 4 shows the results of the formed petri dishes left in an oven at 65 °C for 24hours for the following polymer compositions, in order from left to right in the photograph: 100%PLA, 99% PLA:1% Blend, 99% PLA:1% PHA, 95% PLA:5% Blend, 95% PLA:5% PHA, 70%PLA:30% Blend, and 60% PLA:30% Blend:10% PHA. All of the petri dishes, regardless ofcomposition, had low warpage before the heat treatment testing, as measured by visual observation. After heat treatment, the 100% PLA composition showed significant warpage as measured by visual observation. After heat treatment, the 99% PLA:1% Blend, the 99% PLA:1% PHA, the 95% PLA:5% PHA, and the 95% PLA:5% PHA blend compositions showedmoderate warpage as measured by visual observation. After heat treatment, the 70% PLA:30%Blend, and the 60% PLA:30% Blend:10% PHA compositions showed slight to low warpageunder visual observation.Attorney Docket No. SP24-147

[0120] FIGS. 5A-5D show photographs of formed petri dishes made from either 100%PLA (FIGS. 5A-5B) or 60% PLA:30% Blend:10% PHA (FIGS. 5C-5D), both before heattreatment (FIGS. 5A, 5C) and after heat treatment at 65 °C for 24 hours (FIGS. 5B, 5D). Petri dishes formed from both compositions had low warpage as measured by visual observation before any heat treatment. The dish formed from 100% PLA has significant warpage after heat treatment (FIG. 5B) as seen with visual observation. The dish formed from 60% PLA:30% Blend:10% PHA had slight to low warpage (FIG.5D) under visual observation.

[0121] FIGS. 6A-6D show photographs of discs formed from either 100% PLA (FIGS.6A, 6C) or 70% PLA:30% Blend (FIGS. 6B, 6D) compositions, both before any heat treatment (FIGS.6A-6B) and after sitting in an oven for 24 hours at 65 °C (FIGS 6C-6D). The figures have trace overlays of the articles to better see the warpage before and after head treatment. Although both compositions formed discs with low warpage before heat treatment (FIGS.6A-6B), the 100% PLA disc showed significant warpage after oven treatment (FIG. 6C) while the 70% PLA:30% Blend disc showed slight to low warpage after oven treatment (FIG.6D). Haze

[0122] The haze of the bottoms of the petri dishes from the warpage investigation abovewas investigated by cutting out a 1 mm thick plaque out of the bottom of the dishes and placing them into a UV / vis spectrophotometer. 100% PLA, 99% PLA and 1% Blend, 99% PLA and 1% PHA, 95% PLA and 5% Blend, and 95% Blend and 5% PHA were tested for haze. The 70%PLA and 30% Blend, the 70% PLA 5% PHA, and the 60% PLA and 30% Blend and 10% PHAcompositions were not tested as the haze for these compositions was well over 30% haze as determined by visual observation. To test the haze of the articles, ASTM D1003 (procedure B for spectrophotometer) protocols were followed. The results of the haze tests are summarized in Table 7 below and are shown graphically in FIG. 7.

[0123] Table 7Attorney Docket No. SP24-147

[0124] The dishes formed from 100% polystyrene (PS) had the lowest haze while thosefrom the 100% polypropylene (PP1) had the highest haze. The dishes formed from 100% polylactic acid (100% PLA) had low haze, as did the dishes formed from 99% PLA:1% Blend and 95%PLA:5% Blend. The dishes formed from 99% PLA:1% PHA had slightly higher haze than thepreceding compositions. The dishes formed from 95% PLA:5% PHA had the highest haze of thecompositions tested. Cell Culture Compatibility

[0125] Articles formed into petri dishes with a 35 mm diameter bottom from selectcompositions described in Tables 8-9 below were tissue culture treated, then sanitized and evaluated for cell culture compatibility. Controls for the cell culture compatibility experiments were a petri dish formed from a 100% PLA composition that was tissue culture treated (TCT) with corona discharge and also sanitized, and a commercially available pre-sterilized TCT 6-well tissue culture plate made from polystyrene (Costar®6-well Clear TCT well plate, Cat. No. 3506). As forthe remaining formed petri dishes, one dish’s composition used 95% PLA and 5% PHA, and asindicated in each of Tables 8-9, the remaining two compositions tested contained a blue toner and a stabilizer. The stabilizer was a radiation stabilization package through a vendor. The first composition used 97.5% PLA, 0.5% of a blue toner, and 2% of the stabilizer. The secondAttorney Docket No. SP24-147composition used 97.5% of a mixture of PLA and PHA (the mixture being 95% PLA and 5%PHA), 0.5% of a blue toner, and 2% of a stabilizer. After the PLA dishes and the PLA / PHAdishes were formed, they were tissue culture treated using a corona discharge, and they were then sanitized with 70% ethanol for an hour prior to cell culture testing.

[0126] Cell culture compatibility was evaluated by an article’s ability to attach cells (%attached), the % yield of cells compared to controls, and by how many fold increase in cells were achieved. Two different cell lines were tested for cell culture compatibility. The first cell line was Vero cells (ATCC®, CCLL-81), a hardy line from African green monkey derived kidney epithelial cells. The second cell line was 293T cells (ATCC®, CRL-3216), a more sensitive cell line from human derived kidney epithelial cells. Cells were seeded into either the 35 mm internal diameter formed petri dishes (bottom surface area of 9 cm2) or in individual wells of the 6-well polystyrene control plate (bottom surface are of 9.5 cm2). Vero cells (passage 5) were seeded at 5,000 cells per cm2in 0.22 mL of Dulbecco's Modified Eagle Medium (DMEM) supplemented with 10% fetal bovine-serum (FBS). 293T cells were seeded at 15,000 cells per cm2in 0.2 mL DMEM supplemented with 10% FBS. The articles were then incubated at 37 °C at 5% CO2 for 72 hours. The cultures were then trypsin / EDTA harvested and analyzed for cell recovery and viability with a NucleoCounter®cytometer (ChemoMetec). Both Vero and 293T cells attached to the articles and then expanded, and were able to be harvested from the articles. Results are summarized below in Tables 8-9.

[0127] Table 8Attorney Docket No. SP24-147

[0128] Table 9Example 3 Sterilization

[0129] In a first set of tests, articles were formed from the polymer compositions listed inTables 10-12 below into petri dishes having 1 mm thickness and an internal diameter of 35 mm. Certain compositions included either optical brightener (OB) or blue toner (BT). The dishes were evaluated for color and haze before sterilization using the protocols in ASTM D2244. Color was evaluated using a UV / VIS spectrophotometer (Ultrascan PRO, HunterLabs) using the reflectance setting, specular included. The port size was selected to be 0.39 in. Haze was measured as described earlier above. Next, certain articles were sterilized by high-energy gamma irradiation, and then re-evaluated for haze and color. A summary of results from color and haze measurements are detailed in Tables 10-12 below for both pre- and post-gamma irradiation. In these tables, L*Attorney Docket No. SP24-147 refers to the lightness of the dishes and b* refers to the yellowness of the dishes. FIGS. 8-9 show the graphical results of the color testing in Tables 10-11, while FIG.10 shows the graphical results of the haze testing in Table 12.Attorney Docket No. SP24-147

[0130] Table 10Attorney Docket No. SP24-147

[0131] Table 11Attorney Docket No. SP24-147

[0132] Table 12Attorney Docket No. SP24-147

[0133] The results are shown graphically in FIGS. 8-10 using box plots (also known asbox-whisker plots). Unsterilized dishes with optical brightener or blue toner were less yellow than unsterilized dishes without optical brightener or blue toner. The lightness and haze changed minorly between pre-gamma (unsterilized) and post-gamma (sterilized) dishes. Unexpectedly, the addition of either optical brightener or blue toner resulted in lower yellowing (b*) values after sterilization compared to the unsterilized counterpart, particularly at higher concentrations of PHA that were tested.

[0134] In a second set of tests, articles formed into petri dishes that were 1 mm thick andhad a 35 mm internal diameter from compositions of either 70% PLA:30% PHA or 69.75%PLA:29.75% PHA:0.5% blue toner were photographed both before and after sterilization withgamma irradiation. As shown in FIGS.11A-11D, the pre-sterilized articles (FIGS.11A, 11C) have a yellowish tint regardless of whether blue toner was added to the composition (FIG.11A’s article has no additives, FIG.11C’s article has additives). However, post-sterilization (FIGS.11B, 11D), after the articles had been irradiated with gamma-radiation, the composition comprising blue toner was significantly less yellowed as shown under visual observation (FIG.11D) than either the post- gamma article made from the same composition without additives (FIG. 11B), or the pre-gamma articles having either no additives (FIG.11A) or having additives (FIG. 11C).

Claims

Attorney Docket No. SP24-147 CLAIMS What Is Claimed Is:

1. An article, comprising:PHA, present in an amount from 0.1 wt.% to 40 wt.% based on the total weight of the article; PLA, present in an amount from 60 wt.% to 99.9 wt.% based on the total weight of the article; wherein the article is free of non-biodegradable thermoplastic polymers.

2. The article of claim 1, further comprising PHA, present in an amount from 0.1 wt.% to39.9 wt.% based on the total weight of the article, wherein the total amount of PHA and PHAcombined is 40 wt.% or less the total weight of the article.

3. The article of any one of claims 1 or 2, further comprising at least one additive, present inan amount from 0.1 wt.% to 5 wt.% based on the total weight of the article.

4. The article of claim 3, wherein the at least one additive comprises one or more of anantioxidant, a colorant, an optical brightener, a radiation stability agent, a conductive agent, a nucleating agent, and a clarifying agent.

5. The article of any one of claims 1-4, wherein the article has a flexural strength between10,000 psi and 25,000 psi.

6. The article of any one of claims 1-5, wherein the article has a tensile strain at break ofbetween 5% and 300%.

7. The article of any one of claims 1-6, wherein the article has a tensile stress at break ofbetween 2 ksi and 10 ksi.

8. The article of any one of claims 1-7, wherein the article has b* value for yellowing that isbetween 14 and -5 when the article is 1 mm in thickness.Attorney Docket No. SP24-147 9. The article of any one of claims 1-8, wherein the article has low warpage after 24 hours in an oven at 65 °C.

10. The article of any one of claims 1-9, wherein the article is a tissue culture treated article.

11. The article of any one of claims 1-10, wherein the article has a haze of 50% or less.

12. The article of any one of claims 1-11, wherein the article is a sterilized article.

13. The article of claim 12, wherein the sterilized article is a high-energy irradiated article, and the high-energy irradiation is a dosage between 5 kGy and 50 kGy.

14. The article of any one of claims 1-13, wherein the article is a pipette, a pipette tip, a cell culture plate, a tube, a tube rack, a well plate, an assay plate, a roller bottle, a liquid handling vessel, or a storage vessel.

15. The article of any one of claims 1-14, wherein the article has an L* value for lightness that is between 65-100 when the article is 1 mm in thickness.

16. An article, comprising: PHA, present in an amount from 0.1 wt.% to 40 wt.% based on the total weight of the article; PLA, present in an amount greater than 60 wt.% and less than 99.9 wt.% based on the total weight of the article; and a toner, present in an amount greater than 0 wt.% and less than or equal to 5 wt.%; wherein the article is free of non-biodegradable thermoplastic polymers; and wherein the article has a haze of 50% or less.

17. The article of claim 16, wherein the article is a sterilized article.

18. The article of any one of claims 16-17, wherein the article is a tissue culture treated article.

19. The article of anyone of claims 16-18, wherein the toner is a blue toner.Attorney Docket No. SP24-147 20. The article of claim 17 or 19, wherein the article has a has a b* value that that is at least a value of 0.2 less than the b* value of an unsterilized article having the same composition.

21. The article of any one of claims 16-20, wherein the article has b* value for yellowing that is between 6 and -5, when the article is 1 mm in thickness.

22. The article of any one of claims 16-21, wherein the L* value for lightness is between 65- 95, when the article is 1 mm in thickness.

23. The article of any one of claims 16-22, wherein the article has no visual warpage after 24 hours in an oven at 65 °C.

24. A method of culturing cells, comprising the steps of: providing an article for culturing cells having a composition comprising PHA and PLA,wherein the PHA is present the composition in an amount from 0.1 wt.% to 40 wt.% based onthe total weight of the article, and wherein the PLA is present in the composition in an amount from 60 wt.% to 99.9 wt.% based on the total weight of the article; providing cells of a cell type to the article; and culturing the cells.

25. The method of claim 24, wherein the composition further comprises at least one additive present in an amount greater than 0 wt.% and less than 5 wt.% based on the total weight of the article.

26. The method of any of claims 24-25, wherein the article has 50% haze or less.

27. The method of any of claims 24-26, wherein the article is a sterilized article, a tissue cultured treated article, or a combination thereof.

28. The method of any of claims 24-27, wherein the cells of a cell type are adherent cells.

29. The method of any of claims 24-27, wherein the cells of a cell type are cells that form three-dimensional cell cultures.Attorney Docket No. SP24-147 30. The method of any of claims 24-27, wherein the cells of a cell type are cells that grow in suspension.

31. The method of any one of claims 24-27, wherein the culturing of cells comprises a 2D cell culture, a 3D cell culture, or a suspension culture.

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