Bioplásticos PHB S/A: conceitos básicos e desafios

Sobre a PHB S/A - arquivo 1
1. Conceitos básicos
2. Mercado de Bioplásticos
3. PHA’s e PHB’s
4. PHB Industrial S/A – Brasil
5. Súmula de reunião com a PHB S/A
6. Oportunidades e Objetivos
7. Passos, Riscos e Mitigação
2 TAO biodegradáveis - Sobre a PHB S/A - arquivo 1
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[1] Conceitos básicos: Plásticos
1. Plásticos: materiais orgânicos poliméricos sintéticos. Alto peso molecular (10.000 a 1.000.000 g/mol). São de grande maleabilidade
(plasticidade: propriedade de adaptar-se em distintas formas), facilmente transformável mediante o emprego de calor e pressão.
Os polímeros termoplásticos são compostos de longos fios lineares ou ramificados. A vantagem deste material está na
remodelagem, pois estes plásticos podem ser reciclados várias vezes.
2. Termofixos ou termorrígidos não se alteram com a temperatura. O aumento da temperatura promove a decomposição desses
materiais antes de sua fusão, o que os torna não recicláveis mecanicamente. Isso dificulta a reciclagem destes polímeros. A baquelita
é usada para compor cabos de frigideira por ser dura, resistente e não condutora (o cabo não se aquece no fogo). Poliuretanos (PU),
poliacetato de Etileno Vinil (EVA), resinas poliésteres, resinas epoxi e gelcoat são outros plásticos termofixos. Também são usados
por grifes europeias no acabamento de artigos de luxo de alto valor agregado que demandam alta resistência e durabilidade.
3. Termoplástico é aquele que sob temperaturas relativamente baixas ( 135°C - 250°C) , apresenta alta viscosidade podendo ser
conformado e moldado. Podem ser reprocessados várias vezes, mas obviamente, perdem propriedades a cada reciclagem
podendo também degradar devido ao alto número de re-ciclos. Exemplos de termoplásticos são o polipropileno, o polietileno, o
polimetil-metacrilato (ou acrílico) e o policloreto de vinil (popularmente conhecido como PVC).
4. Polímeros Olefínicos (PO’s) possuem apenas carbono e hidrogênio. São o Polietileno e o Polipropileno. São os mais produzidos
(46%). O PE é dividido em 4 intervalos de densidade g/cm3 (915 < PEBD < 926 < PEMD < 940 < PEAD), que dão aplicações bem
distintas a cada um. Os PE de Baixa Densidade são flexíveis fundem a temperaturas mais baixas. O Polipropileno (910 – 920 g/cm3)
tem alta resistência a fratura (dobradiço), mas fica quebradiço se congelado (Tupperware). Tecido não-tecido, Ráfia (Sacos para
grãos e fertilizantes), Fibras, Cadeiras, Brinquedos, Copos Plásticos, Recipientes para alimentos, remédios e produtos químicos,
Corpo de eletrodomésticos, Carpetes, Seringas de injeção, Material hospitalar esterilizável, Autopartes (parachoque e interiores).
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polyester, polyamide & acrylic fibers
polyurethane
polyethylene terephthalate
polyvinylchloride
polystyrene
polypropylene
highdensity polyethylene
low-density & linear low-density polyethylene
150/400 = 38%
https://advances.sciencemag.org/content/3/7/e1700782/tab-figures-data
Global Primary Plastics Production in million of tonnes ...
... according to industrial use ... according to type of
polymer
Polyolefines
185/400 = 46%
Growth level in 45 years
World GDP: 4.5x
Ammonia (80% in fertilizers):
3.6x
Cement (construction): 6.6x
Plastics: 10.4x
https://www.iea.org/petrochemicals
IEA forecast for oil demand
growth
2017 – 2030 (M barrels a day)
8,300 Mt of plastics produced from 1905 to 2015
5,000 Mt (60%) discharged in landfills or environment
2,500 Mt (30%) still in use (including 9% recycled)
800 Mt (10%) incinerated
3,800 Mt (45%) made in the last 13 years
Average growth is 8.5% annually
This is higher than cement or steel

[1] Conceitos básicos: Bioplásticos
5. Bioplásticos: Quando é 100% derivado de biomassa (bio-based), e não de petróleo, E/OU quando é biodegradável.
6. Biodegradação: é o reconhecimento (quebra) de substâncias orgânicas por enzimas presentes na natureza. A estrutura molecular é
transformada em OUTRAS substâncias básicas (mineralização), como água, dióxido de carbono e metano, através de processos
metabólicos ou enzimáticos de fungos ou bactérias, que usam essa substância orgânica como fonte de carbono e energia. Tanto a
quebra física em pedaços menores, quanto a degradação química em substancias básicas, em menos de 1 ano, são necessárias para o
processo ser considerado biodegradação. É processo oposto à fotossíntese com metabolismo celular contínuo. Tem 3 etapas:
a) Biodeterioração é a degradação na superfície, quando da exposição a fatores abióticos no ambiente externo (que influenciam a
população de microorganismos). Modifica a natureza mecânica, física e química da matéria e enfraquece a estrutura do material.
Alguns fatores abióticos são a compressão (mecânica), luz (UV), temperatura e estado químico do ambiente (salinidade, pH, etc.).
b) Biofragmentação: quebra do material (degradação física) em pedaços menores, mantendo as polímeros no seu tamanho original.
c) Assimilação: microorganismos excretam enzimas para quebrar os polímeros (degradação química) em partes menores (oligômeros
e monômeros), solúveis em água e que atravessem a parede celular. Dentro delas, eles entram nas vias catabólicas que levam à
produção de energia (ATP) e elementos da estrutura celular. Deste metabolismo resultam CO2 (com ou sem CH4) e H2O.
7. A quebra de materiais por microorganismos com O2 é a digestão aeróbica e sem O2 é a digestão anaeróbica. As reações
anaeróbicas produzem metano e as reações aeróbicas não. Mas ambas produzem CO2, água, algum tipo de resíduo e uma nova
biomassa. A reação aeróbica ocorre mais rápido que a anaeróbica. Mas a anaeróbica reduz mais o volume e a massa do material.
8. Compostagem é o conjunto de técnicas aplicadas para estimular a decomposição de materiais orgânicos por microorganismos
aeróbios para obter, no menor tempo possível, um material estável, rico em húmus e nutrientes minerais com atributos físicos,
químicos e biológicos superiores (sob o aspecto agronômico) àqueles encontrados na matéria-prima. Além de proteger o ambiente
(menos lixo orgânico), a compostagem gera um produto de valor, o composto, que é um ótimo fertilizante natural.
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9. As petroquímicas intencionalmente cunharam uma ambiguidade na
definição de “bioplástico” e de “biodegradável”. Isto deu status de
bioplástico para polímeros de petróleo que são compostáveis
(mesmo não sendo naturalmente degradáveis) e polímeros de
biomassa que não são compostáveis (e portanto não são naturalmente
degradáveis). A figura criada pela European Bioplastics (associação
mormente patrocinada por petroquímicas, inclusive Braskem) é
amplamente divulgada, servindo para consolidar a ambiguidade.
10. Uma prova do interesse em reduzir a objetividade da informação ao
público é que, apesar da definição formal de bioplástico exigir que o
material seja OU bioderivado OU compostável (o que NÃO é
degradação natural), a figura de doutrinação traz o termo
biodegradável, em vez do termo compostável. Tal confusão é do
interesse das petroquímicas, pois gera falso apelo de sustentabilidade
a polímeros (de petróleo ou de biomassa) que causarão os mesmos
problemas quando tiverem o mesmo destino que os centenas de
milhões de toneladas de plásticos convencionais anualmente
transferidos ao solo, rios e oceanos.
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11. Os regulamentos e leis para produtos e processos industriais se baseiam em normas técnicas, as quais definem limites e métodos
de medição para evitar má conduta ou concorrência desleal. Entretanto, embora seja um processo muito bem conhecido e
previsível, a biodegradação (fungos e bactérias) não é um processo industrial e pode variar com os fatores ambientais que
influenciam a dinâmica dos microorganismos. Apesar de tal variação ser conhecida, isto deu margem a que a indústria petroquímica
se antecipasse e, por meio de sua capacidade de moldar fenômenos institucionais, ela cunhasse as normas técnicas de bioplásticos
retirando biodegradável e colocando compostável como requisito para o termo bioplástico.
12. Aquela que é (por enquanto) a mais difundida é a norma EN 13432: “Requisitos para embalagens recuperáveis através de
compostagem e biodegradação - Esquema de ensaio e critérios de avaliação para a aceitação final da embalagem”. Até o nome
causa confusão, pois sugere que ela certifica polímeros que se biodegradam, gerando falsa noção de degradação no meio ambiente,
quando na verdade ela só trata de polímeros compostáveis, ou seja, que se biodegradam em condições industriais de temperatura
e homogeneidade da massa cozida (degradada) as quais não ocorrem no meio ambiente. A norma em si não é um problema, pois
apenas determina requisitos para a um certo tipo de reciclagem industrial de materiais que ocorre em uma condição restrita. O
problema é o uso intencionalmente errôneo da norma, ao transformá-la na principal referência sobre a sustentabilidade dos
plásticos, por meio da massiva divulgação e da certificação de produtos e embalagens por meio dela, consolidando noções
errôneas no consumidor sobre a sustentabilidade (degradabilidade nas várias condições naturais) dos polímeros abrangidos por ela.
13. Sustentabilidade: Em 1972: atendimento das necessidades presentes sem comprometer a capacidade das gerações futuras de
atender suas necessidades. Em 2002: melhoria da qualidade de vida de todos os habitantes do mundo sem aumentar o uso de
recursos naturais além da capacidade da Terra (em ofertar e recompor).
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14. Há uma dificuldade maior em criar normas de padronização para a biodegradação em meio natural, pois, cada bioma tem um grande
número de combinações de variáveis ambientais que afetam o metabolismo microbiano (temperatura, pH, incidência de UV,
salinidade umidade, etc.). Ainda assim, já existem várias normas que estabelecem critérios para definição de degradabilidade de
plásticos em meio natural. Um ponto de partida são as normas para biodegradabilidade de plásticos em esgoto, vistas abaixo:
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Fonte: Harrison, J.P. et al. Biodegradability standards for carrier bags and plastic films in aquatic environments: a critical review. Royal Society Open Science 5 (5), May 2018.

[1] Conceitos importantes : Bioplásticos
9. Há uma dificuldade maior em criar normas de padronização para a biodegradação em meio natural, pois, cada bioma tem um grande
número de combinações de variáveis ambientais que afetam o metabolismo microbiano (temperatura, pH, incidência de UV,
salinidade umidade, etc.). Ainda assim, já existem várias normas que estabelecem critérios para definição de degradabilidade de
plásticos em meio natural. Cada norma ainda foca em uma combinação específica de variáveis ambientais:
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there are very few industrial composting facilities available. Moreover, as it is difficult and expensive to separate
compostable plastics from other plastics, many industrial composters do not want plastic of any kind in their
feedstock. Home composting of plastic packaging is dangerous and should not be encouraged, as it is often
contaminated with meat, fish, or poultry residues, and temperatures do not rise high enough to kill the pathogens.
is based on measuring the emission of carbon dioxide during degradation. Hydro-biodegradable plastic is compliant
with EN 13432, precisely because it emits CO2 (a greenhouse gas) at a high rate
If a leaf were subjected to the CO2 emission tests included in EN13432 it would not be considered biodegradable or
compostable!
Another problem with EN 13432 is that it requires almost complete conversion of the carbon in the plastic to CO2,
thus depriving the resulting compost of carbon, which is needed for plant growth, and wasting it by emission to
atmosphere
Conversion of organic materials to CO2 at a rapid rate during the composting process is not "recovery" as required
by the European Directive on Packaging and PackagingWaste (94/62/EC as amended), and should not really be part
of a standard for composting. Nature's lignocellulosic wastes do not behave in this way, and if they did the products
would have little value as soil improvers and fertilisers, having lost most of their carbon.

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IUPAC is the universally-recognized authority on chemical nomenclature and
terminology and two IUPAC bodies take leading roles in this activity: Division
VIII – Chemical Nomenclature and Structure Representation and the Inter-
divisional Committee on Terminology, Nomenclature, and Symbols. As one
of its major activities, IUPAC develops Recommendations to establish
unambiguous, uniform, and consistent nomenclature and terminology for
specific scientific fields, usually presented as: glossaries of terms for specific
chemical disciplines; definitions of terms relating to a group of properties;
nomenclature of chemical compounds and their classes; terminology,
symbols, and units in a specific field; classifications and uses of terms in a
specific field; and conventions and standards of practice for presenting data
in a specific field. The Recommendations are published in the IUPAC journal,
Pure and Applied Chemistry (PAC) and journal issues are freely-available in the
year following their publication. They also appear in the IUPAC Standards
Online database one year after publication in PAC. Information on chemical
terminology can also be accessed through the IUPACColor Books.
IUPAC’s webpage

Globally Official Definitions (IUPAC)
“Scientists and users of other fields of application have often developed incoherent terminologies. The aim of the following
recommendations is to provide a terminology usable without any confusion in the various domains dealing with biorelated polymers,
namely, medicine, pharmacology, agriculture, packaging, biotechnology, polymer waste management, etc. This is necessary because:
(i) human health and environmental sustainability are more and more interdependent;
(ii) research, applications, norms, and regulations are still developed independently in each sector;
(iii) nonspecialists like journalists, politicians, and partners of complementary disciplines are more and more implicated and need a
common language. ”
[x] means the source of the doctrine, as numbered in the bibliographic list at the end of the publication.
plastic
Generic term used in the case of polymeric material that may contain other substances to improve performance and/or reduce costs.
Note 1: The use of this term instead of polymer is a source of confusion and thus is not recommended.
Note 2: This term is used in polymer engineering for materials often compounded that can be processed by flow.
biobased
Composed or derived in whole or in part of biological products issued from the biomass (including plant, animal, and marine or forestry materials).
Note: A biobased polymer or polymeric device is not necessarily environmentally friendly nor biocompatible nor biodegradable, especially if it is
similar to a petro-based (oil-based) polymer.
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Michel Vert, Yoshiharu Doi,
Karl-Heinz Hellwich, Michael Hess,
Philip Hodge, Przemyslaw Kubisa,
Marguerite Rinaudo, François Schué

environmentally friendly ; ecocompatible
Qualifiers for a substance, device, or process that has minimal deleterious impact on the environment, which is air, water, minerals, living systems,
etc.
Note 1: The assignment of these qualifiers to a polymer must be based on a consistent life cycle assessment.
Note 2: Ecocompatible is introduced to complement biocompatible, whose meaning is limited to living systems.
life cycle assessment
Investigation and valuation of the environmental impacts of a given product or service caused or necessitated by its existence [2].
Note 1: Also known as life cycle analysis, LCA, ecobalance, and cradle-to-grave analysis.
Note 2: Assessing the life cycle of a polymer or a plastic must take into account all the factors that can be identified from the up-stage raw material
to the waste management.
bioplastic
Biobased polymer derived (only) from the biomass or issued from monomers derived from the
biomass and which, at some stage in its processing into finished products, can be shaped by flow.
Note 1: Bioplastic is generally used as the opposite of polymer derived from fossil resources.
Note 2: Bioplastic is misleading because it suggests that any polymer derived from the biomass is environmentally friendly.
Note 3: The use of the term “bioplastic” is discouraged. Use the expression “biobased polymer”.
Note 4: A biobased polymer similar to a petrobased one does not imply any superiority with respect to the environment unless the comparison of
respective life cycle assessments is favourable.
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composting
Process of biological decomposition of organic matter performed by microorganisms, mostly bacteria and fungi. (See biodegradation.)
Note 1: Modified from [10] to be more general.
Note 2: Composting can be performed industrially under aerobic or anaerobic conditions or individually (home-composting).
Note 3: If present, earthworms also contribute to composting. They are sometimes cultured purposely in industrial composting facilities. One often
talks of lombri-composting.
disintegration
Fragmentation to particles of a defined size [9].
Note: The limiting size is generally defined according to sieving conditions.
fragmentation
Breakdown of a material to particles regardless of the mechanism and the size of fragments.
Note: Modified from [9] in order to remove size limitation. (See disintegration.)
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deterioration
Deleterious alteration of a material in quality, serviceability, or vigor.
Note 1: Deterioration can result from physical and/or chemical phenomena.
Note 2: Deterioration is connected to a loss of performances and thus to the function, whereas degradation is connected with a loss of properties.
Note 3: Polymer deterioration is more general than polymer degradation, which reflects loss of properties resulting from chemical cleavage of
macromolecules only. (See degradation.)
degradation
Progressive loss of the characteristics of a substance or a device. (See degradable.)
Note: Degradation caused by the action of water is termed “hydrodegradation” or hydrolysis; by visible or ultraviolet light is termed “photo - degradation”; by
the action of oxygen or by the combined action of light and oxygen is termed “oxidative degradation” or “photooxidative degradation”, respectively; by
the action of heat or by the combined effect of chemical agents and heat is termed “thermal degradation” or “thermochemical degradation”,
respectively; by the combined action of heat and oxygen is termed “thermooxidative degradation”.
degradation (biorelated polymer)
Degradation that results in desired changes in the values of in-use properties of the material because of macromolecule cleavage and molar mass decrease.
Note 1: Adapted from [8] where the definition is general. For biorelated polymers, the definition is purposely and specifically limited to the chemical
degradation of macro - molecules in order to make a clear distinction with the physical degradation of the material. (See fragmentation and
disintegration.)
Note 2: In any condition, degradation must be used instead of biodegradation when the mechanism of chain scission is not known or proved as cell-mediated.
Note 3: Degradation can result from action of enzymes (see enzymatic degradation), or from action of organisms, and/or microorganisms. (See
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erosion
Degradation that occurs at the surface and progresses from it into the bulk.
Note 1: Modified from [9] to be more precise.
Note 2: See enzymatic degradation. In the case of polymers, water-soluble enzymes can hardly diffuse into the macromolecular network, except,
maybe, in some hydrogels. They adhere to surfaces to cause erosion.
Note 3: Erosion can also result from chemical degradation when the degrading reagent reacts faster than it diffuses inside. There is a risk of
confusion that can be eliminated after careful and detailed investigation of the degradation mechanism. (See bioerosion.)
Note 4: The wording bulk erosion is incorrect and its use therefore discouraged.
mineralization
Process through which an organic substance becomes impregnated by or turned into inorganic substances.
Note 1: A particular case is the process by which living organisms produce and structure minerals often to harden or stiffen existing tissues. (See
biomineralization.)
Note 2: In the case of polymer biodegradation, this term is used to reflect conversion to CO2 and H2O and other inorganics. CH4 can be considered as
part of the mineralization process because it comes up in parallel to the minerals in anaerobic composting, also called methanization [9].
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biodegradable (biorelated polymer)
Qualifier for macromolecules or polymeric substances susceptible to degradation by biological activity by lowering of the molar masses of
macromolecules that form the substances.
Note 1: Adapted from [8] to include the notion of decrease of molar mass in the definition.
Note 2: It is important to note that in the field of biorelated polymers, a biodegradable compound is degradable whereas a degradable polymer is not
necessarily biodegradable.
Note 3: Degradation of a polymer in vivo or in the environment resulting from the sole water without any contribution from living elements is not
biodegradation. The use of hydrolysis is recommended. (See also degradation.)
ultimate biodegradation
Complete breakdown of a compound to either fully oxidized or reduced simple molecules (such as carbon dioxide/methane, nitrate/ammonium, and
water) [2].
Note 1: This term reflects the end-products of biodegradation. As such, it differs from the theoretical degree of biodegradation, which depends on the
presence of non-biodegradable components.
Note 2: The use of this expression is not recommended.
maximum degree of biodegradation
Greater value of the degree of biodegradation that can be reached under selected experimental conditions [9].
Note 1: This expression reflects the fact that some biodegradable parts of a biodegradable material may not be accessible to biodegradation.
Note 2: Not to be confused with ultimate degradation.
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biodegradation (biorelated polymer)
Degradation of a polymeric item due to cell-mediated phenomena [9].
Note 1: The definition given in [2] is misleading because a substance can be degraded by enzymes in vitro and never be degraded in vivo or in the
environment because of a lack of proper enzyme(s) in situ (or simply a lack of water). This is the reason why biodegradation is referred to as
limited to degradation resulting from cell activity. (See enzymatic degradation.) The definition in [2] is also confusing because a compounded
polymer or a copolymer can include bioresistant additives or moieties, respectively. Theoretical biodegradation should be used to reflect the
sole organic parts that are biodegradable. (See theoretical degree of biodegradation and maximum degree of biodegradation.)
Note 2: In vivo, degradation resulting solely from hydrolysis by the water present in tissues and organs is not biodegradation; it must be referred to
as hydrolysis or hydrolytic degradation.
Note 3: Ultimate biodegradation is often used to indicate complete transformation of organic compounds to either fully oxidized or reduced simple
molecules (such as carbon dioxide/methane, nitrate/ammonium, and water. It should be noted that, in case of partial biodegradation, residual
products can be more harmful than the initial substance.
Note 4: When biodegradation is combined with another degrading phenomenon, a term combining prefixes can be used, such as oxo-biodegradation,
provided that both contributions are demonstrated.
Note 5: Biodegradation should only be used when the mechanism is proved, otherwise degradation is pertinent.
Note 6: Enzymatic degradation processed abiotically in vitro is not biodegradation.
Note 7: Cell-mediated chemical modification without main chain scission is not biodegradation. (See bioalteration.)
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sustainability
Developments that meet the needs of the present without compromising the ability of future generations to meet their needs [15].
Note: Other definitions are not recommended in the context of biorelated polymers.
green chemistry ; sustainable chemistry
Design of chemical products and processes that reduce or eliminate the use or generation of substances hazardous to humans, animals, plants, and the
environment.
Note 1: Modified from [14] to be more general.
Note 2: Green chemistry discusses the engineering concept of pollution prevention and zero waste both at laboratory and industrial scales. It encourages the
use of economical and ecocompatible techniques that not only improve the yield but also bring down the cost of disposal of wastes at the end of a
chemical process.
green polymer
Polymer that conforms to the concept of green chemistry.
Note: Green polymer does not necessarily mean environmentally friendly polymer or biobased polymer although the confusion is often made in the literature.
environmentally degradable polymer
Polymer that can be degraded by the action of the environment, through, for example, air, light, heat, or microorganisms [8].
Note: When it is to be a source of material, such a polymer must be designed to degrade into products at a predictable rate compatible with the application.
Such products are usually of lower molar mass than the original polymer.
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litter
Solid waste carelessly discarded outside the regular garbage and trash collection [10].
microparticle
Particle with dimensions between 1 × 10−7 and 1 × 10−4 m.
Note 1: The lower limit between micro- and nano-sizing is still a matter of debate. (See nanoparticle.)
Note 2: To be consistent with the prefix “micro” and the range imposed by the definition, dimensions of microparticles should be expressed in μm.
nanoparticle
Particle of any shape with dimensions in the 1 × 10–9 and 1 × 10–7 m range.
Note 1: Modified from definitions of nanoparticle and nanogel in [2,3].
Note 2: The basis of the 100-nm limit is the fact that novel properties that differentiate particles from the bulk material typically develop at a critical
length scale of under 100 nm.
Note 3: Because other phenomena (transparency or turbidity, ultrafiltration, stable dispersion, etc.) are occasionally considered that extend the
upper limit, the use of the prefix “nano” is accepted for dimensions smaller than 500 nm, provided reference to the definition is indicated.
Note 4: Tubes and fibers with only two dimensions below 100 nm are also nanoparticles.
mulching film
Polymer film aimed at covering seeded area in order to protect the growing plants from weeds and cold and preserve humidity.
Note: Such film acts as a mobile green house.
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ASTM: American Society for Testing and Materials

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Bioplásticos PHB S/A: conceitos básicos e desafios

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