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Vous êtes ici : Accueil > Technique > Mémoires > Nanocellulose: a solution to improve oxygen scavenger in active packaging Révision : 13 décembre 2018  
Nanocellulose: a solution to improve
oxygen scavenger in active packaging
             Oihana CAZABAN et Martin VIEILLE
Élèves ingénieurs 2e année
Mai 2016
Mise en ligne - Décembre 2018
Ce mémoire d'étudiants est une première approche du sujet traité dans un temps limité.
À ce titre, il ne peut être considéré comme une étude exhaustive comportant toutes les informations
et tous les acteurs concernés.
I - Introduction
II - Technical analysis
III - Economical analysis
IV - Future prospects
V - Conclusion
VI - Bibliography-Webography
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I - Introduction


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            Emballage alimentaire      
  Food packaging

Food is essential for human-being, scarce and very valuable. While 870 million people are starving, 1.3 billion tons of food are wasted. The consequences of global food waste are not only economic – $ 750 billion lost – but also environmental because it is responsible for the emission of 3.3 billion tonnes of greenhouse gases.

Then, protecting food is necessary. Development of new packaging materials could be an efficient solution to deal with this problem. Manufacturers are looking for efficient, durable, lightweight and competitive packaging. On the one hand, the European Union has put in place legislation (1994) to reduce the weight and volume of packaging, to promote their recycling to limit their waste and their impact on the environment. On the other hand, each member state has also established its own laws such as the "Grenelle de l'environnement" in France.

In fact, most of packaging are currently made of plastic or of a combination of cardboard and polymer often derived from oil. Henceforth, the urgent need to implement sustainable development is fueling industrial interest in alternative materials from renewable resources. Moreover, the use of nanoparticles is promising for the development of lighter and stronger materials with improved functions. Consumers are looking for their safety. Despite regulations, the risk of food poisoning is still present in developed nations and emerging countries, and sometimes, it can be dramatic.

Food waste, environmental impact and consumer safety are the three main ideas that researchers are working on. New active packaging solutions are then expecting in response to consumers demands.

II - Technical analysis


II-1 - Active packaging

II-1-1 - Functional packaging

Two kinds of functional packaging can be distinguished: intelligent and active packaging.

                Active and intelligent packaging     
[Pol. J. Food Nutr. Sci., 2014]

Two regulations of the European Parliament and of the Council oversee the actions of producers, distributors or any person in relation to food packaging. They are intended to ensure that the agri-food industry does nothing that harms the health of consumers.

Regulation (EC) N°1935/2004 - 27 October 2004: it aims at securing an high level of protection of human health by establishing rules applicable to materials and articles which, in their finished state:

Regulation (EC) N°450/2009 - 29 May 2009: it sets out requirements for the marketing within the European Community of active and intelligent materials and articles intended to come into contact with food.

II-1-2 - Main purposes

Food packaging exists since Prehistory: food was kept and transported in animal skin, bottle, calabash, tissue, basket or pottery.

In 1809, the invention of the tin can revolutionizes the preservation of food, even if freezing, salting or drying already exists. The packaging evolved with better blocking effects of moisture, CO2, O2, water and other liquids, and UV light which are responsible to the food degradation. From a century, many chemical agents for food preservation are introduced in industrial food, like nitrates, sulfites, sorbic or benzoic acid.

The goal of active packaging is to protect, secure, increase the shelf life while maintaining the quality of food. Several solutions can be used:

These products are used alone or in any combination. Functional packaging development in the European Union only started in the 21st century, whereas in Japan, Australia and the United States, it started in the 1970s.

There are two main ways of making an active packaging:

                Oxygen in food packaging  
  Oxygen in food packaging causes
different issues for food and bacteria development

One solution is to limit the level of oxygen. This is why the oxygen scavenger is integrated into the packaging to extend the shelf life of the food and allow the consumer to keep the product longer. As part of these preservatives, Japan's Mitsubishi Gas Chemical discovered ferrous oxygen scavengers in 1976 with the Ageless Group. However, these sensors could be enzyme or polymer that has a better kinetic absorption.

To protect food with oxygen scavenger, first possibility is the common "1 in 2 solution": oxygen scavenger sachet with food into traditional packaging. Second possibility is “2 in 1 solution":

  Methods for adding an oxygen scavenger into a food package

II-1-3 - Oxygen scavenger

Oxygen scavenger or oxygen absorber is added to enclosed packaging to help remove or decrease the level of oxygen in the package. It's used to help maintain product safety and extend shelf life.

"1 in 2 solution" (one active packaging in two pieces)

  Oxygen scavenger sachet is the most common solution

0xygen scavengers:

These systems are shaped:

  Cryovac® OS Films begin scavenging on demand
after triggering the UV light process
[Meat and Livestock Australia Limited]

Cryovac's innovation: this polymer film binds the surrounding oxygen during activation of the UV light. The bag consists of a polypropylene network or a liquid impervious protective film.

Oxygen scavenger sachet: iron scavenger

Chemical reaction: iron oxidation Fe + O2 + H20 → Fe (OH)3 combined system 4FeCO3 + 6 H20 +O2 → 4 Fe(OH)3 + 4 CO2

Application: 1g of iron absorbs 0.134 mol of oxygen, it's 324 cm3 at 25°C like a beef punnet in supermarket.

Oxygen scavenger sachet: enzyme scavenger

Chemical reaction: 2 Glucose + 2O2 + 2 H2O → 2 acid D gluconique + 2H2O2 2H2O2→ 2H20 + O2

Application: 1g of glucose absorbs 62.2 cm3 of oxygen at 25°C, five times less than iron scavenger to conserve beef punnet.

Oxygen scavenger as film or holder

Chemical reaction:

O2 → O2 absorbs in film or polymer punnet.


    UV light

Application: not found.

Another solution is to replace the normal atmosphere with a controlled gas (a mixture of oxygen, nitrogen and carbon dioxide). This modification avoids the degradation of food in an environment conducive to bacterial contamination.

  Non-exhaustive list of oxygen scavengers producers  

"2 in 1 solution": two actions in one packaging

There is an interesting alternative to the "1 in 2 solution": to integrate the active agent into the packaging. Thus, consumers are not disturbed by the presence of unknown additives in the sachet. In addition, this alternative simplifies the technology of industrial packaging.

II-1-4 - Environmental aspects

Environmental law reforms impose stricter regulations on manufacturers.

Active packaging minimizes the impact on the environment.

II-2 - Nanocellulose

In 1977, three scientists of the ERD lab in New Jersey discovered cellulose nanofibrils (CNF) introducing cellulose in a milk homogenizer which imposes high pressure, high shear force and numerous collisions. Cellulose nanocrystals (CNC) were discovered in the 50s.

II-2-1 - Cellulose

Cellulose is a plant-based polymer found in the cell membranes of all plants and trees. It is therefore the main constituent of plants, especially wood. It is also the most abundant organic matter on Earth, accounting for more than 50% of the biomass. It is estimated that the plants of our planet synthesize between 50 and 100 billion tons per year.

It is the most present component in the cell wall. More precisely, it is a linear homopolysaccharide of β-1.4-linked anhydro-D-glucose units with a DP of 10000. The main differences between cellulose nanoparticles are steps involved in their preparation. To prepare nanocellulose, put fibers in suspension; an alcalin treatment is done at 80°C and 4 % of NAOH.

  Arrangement of fibrils, microfibrils and cellulose in cell walls
[Int. J. of Ph.]

II-2-2 - Microfibrils

Microfibrillated cellulose (MFC) is composed of expanded high-volume cellulose, moderately degraded and greatly expanded in surface area. Its diameter is about 20–60 nm and it has a length of several micrometers. The specific area of sisal MFC is around 50 m²/g, which is about 10 times greater than natural fibers. Unlike cellulose nanocrystal (CNC), MFC presents both amorphous and crystalline parts and presents a web-like structure. It is obtained by the mechanical disintegration of cellulosic materials without use of hydrolysis.

  Stucture of cellulose. (a) Cellulose fibers from a ponderosa pine.
(b) Macrofibrils compose each fiber.
(c) Each macrofibril is composed of bundles of microfibrils.
(d) Microfibrils, in turn, are composed of bundles of cellulose chains.
[Nutrition resources]
  Microscopic image of cellulose microfibrils

Microfibrillated cellulose is currently manufactured from several cellulosic sources and then its properties depend on it. Wood, the most important industrial source of cellulosic fibers, is the main raw material used to produce MFC.

MFC manufacturing

  The most applied mechanical treatment processes used in the manufacturing
of microfibrillated cellulose: the homogenizer, the microfluidizer and the grinder

First of all, its higher aspect ratio could be more profitable for the development of barrier materials. Secondly, MFC is more appropriate for the papermaking market with lower cost. Indeed, the yield of the mechanical process is 100 %

II-2-3 - Cellulose whiskers

Many terms are used to refer to cellulose nanocrystal: rod-like colloidal particle, nanocrystalline cellulose, cellulose whisker, cellulose microcrystallite, microcrystal, microfibril, etc. We call them CNC here.

  Part of a cellulose fiber where the crystalline and non-crystalline regions are shown.

To product CNC, the main process is based on strong acid hydrolysis under strictly controlled temperature conditions, agitation and time. Amorphous regions, considered as structural defects, are attacked during the acid hydrolysis, leaving crystalline regions, more resistant, intact.

They are very small particles. Diameter: 5-10 nm ; length: 100-500 nm. The CNC geometrical dimensions vary widely according to the source of cellulosic material and hydrolysis conditions. "Concerning the CNC mechanical properties, its Young’s modulus is estimated between 130 GPa (Sakurada et al., 1962) and 250 GPa (Zimmermann et al., 2004): this value is closed to the modulus of a perfect crystal of native cellulose (167.5 GPa according to Habibi et al., 2010 and Tashiro and Kobayashi, 1991)".

  Main producers of CNC  

The CNC production is mainly localized in Northen Europe countries and Canada, with a strong forest industry and great cellulose knowledge.

II-2-4 - Nanocellulose: oxygen barrier

The good oxygen barrier properties of nanocellulose can be attributed to the dense network formed by nanofibrils with smaller and more uniform dimensions. The dense nanofibrils form more complex and smaller pores compared to pure cellulose fibers which are in micro scale. CNC has higher crystallinity than CNF but CNF layer has less oxygen permeability than CNC. Both showed similar solubility, but oxygen molecules penetrate more slowly though the CNF layer because of its structure. CNF film has higher entanglements within the layer which increase the tortuosity factor or the diffusion path.

  Shows schematic representation of increased diffusion path within the nanocellulose films.

Nanocellulose can be used as film, coating or filler material to obtain a composite. The recommended oxygen transmission rate (OTR) for modified atmosphere packaging is below 10–20 ml.m-2day-1 (Parry 1993). Saito and Isogai showed OTR for the MFC film with thickness of 21 μm is as low as 17 ± 1 ml m-2 day-1. Compared to synthetic polymer film with the same thickness, MFC film is competitive with best synthetic polymers with respect to oxygen transmission rate (PVdC coated, oriented polyester and EVOH). A drawing on Figure n°11 explains the functioning of a nanocellulose coat which gives of a packaging its properties of gas impermeability.

  Oxygen permeability of nanocellulose film compared to those made form
commercially available petroleum based materials and other polymers.

CNF is also used as filler material to obtain a nanocomposite material. Plackett [et al.] show that addition of 15 wt% of CNF substantially increases the oxygen barrier of amylopectin film. The use of CNF in xylan film shows very low oxygen permeability of 0.19 cm3 μm m-2 day-1 kPa, which is comparable to previously reported values for 100% CNF film. Nanocellulose has impermeability properties close to the best impermeable material. Even though the oxygen barrier properties of CNF film, layer or filler are competitive with current commercial films made from synthetic polymers, their water vapor barrier remains very low (or the water vapor transfer rate remains very high).

II-3 - Nanocellulose in order to improve oxygen' scavengers

Nanocellulose and oxygen's scavengers combination is a development path for active packaging particularly for the oxygen level control in packaging in order to preserve the perishable food's lifetime. Different solutions are considered in this study.

II-3-1 - Nanocellulose and oxygen's scavenger blend coated on packaging

Molecule grafting on nanocellulose without release of components improves capacity of oxygen adsorption while allows the contact between the oxygen's scavenger and the food. So, this blend could be coated close to the food.

II-3-2 - Nanocellulose and oxygen's scavenger blend introduced into the packaging matrix

For example, a blend of polymer like PLA (biodegradable polymer) and nanocellulose to conceive a totally biodegradable packaging but with properties which increase the food product's shelf-life. The principle is to produce a packaging with a material directly with the properties necessary to capture oxygen. In fact, strategy is to design an active packaging introducing oxygen scavengers in nanoporous nanofibrils network without using any other chemicals. When oxygen crosses the packaging wall, it is captured by active agents. These last are mixed with nanocellulose in polymer matrix. The goal is to give some specific area to oxygen' scavengers and develop their properties. But if the packaging is damaged, there is no salting out of the active agents because they are fixed on nanocellulose. Like this, oxygen is picked up during the crossing of the packaging wall and oxygen's concentration is controlled into the food packaging.

II-3-1 - Surface modification of the packaging by nanocellulose functionalized with oxygen scavengers

The principle is to graft oxygen scavenger on nanocellulose and like this make the salting out impossible. The nanocellulose's functionalization is achieved by its surface modification. It can be done by either physical interactions or absorption of molecules onto its surface or by using a chemical to achieve covalent bonds between nanocellulose and grafting agent. Then, this new product is introduced in food packaging either by coating or like a gel in a little cap. Oxygen can pass through the wall of the package but, once inside, the active agents grafted onto the nanocellulose can capture it. So this solution does not prevent the oxygen to cross the packaging'wall but regulates its concentration in the atmosphere of food product.

III - Economical analysis


III-1 - Markets' characterization

Excluding packaging machinery, the global packaging industry turnover is around 797 billions of dollars in 2013 and will grow at an annual rate of 4 % to 2018. According to the report "The Future of Global Packaging to 2018", packaging sales are concentrated in Asia, which accounted for 36 % of the global market in 2012. North America and Europe share respectively 23 % and 22 %. According to the report, this trend will change and Asia will represent 40 % of the market and the part of Europe and North America will lose out.

III-1-1 - Food packaging

Furthermore, this report also shows that 51 % of the packaging materials are allocated for food and 18 % for beverage. With the increasing diversity of food products, consumers ask for more packaging solutions adapted to each product. The market is sectorized in four main kinds of packaging: paper / paperboard, plastic, metal and glass. It's quite difficult to obtain the updated data regarding the market share of food packaging materials of the current year. Plastic and paper & board are the most present materials in the packaging market.

  Market share of packaging material
[Food Packaging Forum]

For several years, the use of glass and metal is decreasing. There are now limited to beverage. In fact, the price of these raw materials is higher than paper and plastic. In the 1980’s, plastic packaging has been a revolution. It presents good barrier and mechanical properties, so it could be the best food packaging. Unfortunately, its environmental impact is a strong weakness in society where biosourced and biodegradable materials are now preferred. Furthermore, its price depends on petroleum's price and its coming soon shortage, researchers are looking for alternatives. Paper and cardboard have interesting mechanical properties but are too sensitive to moisture and water. Nevertheless, they are ecological and cheaper.

Societal requirements in terms of sustainability must be taken into account in the choice of packaging materials. Biobased and biodegradable materials should be the future of packaging. For a study conducted in France (Glineur, 2012), packaging companies were asked about the classification of the main innovation axes of their future products. In first place comes recyclability (56%) followed by ease of use (48%).

Another survey (Dupont, 2012) can be looked at. Packaging industries were asked to attribute the two key trends that will impact the packaging market within the next ten years. Respondents say cost is the top factor driving the industry today (59 %) but they predict it will fall significantly in importance in 10 years (dropping 28 %) to below factors like sustainability (51 %) and food safety/security (37 %) according to the Figure n°14. Future trends in Europe are sustainability (53 %) and food safety and security (40 %) whereas future trends in North America are sustainability (48 %) and cost (41 %).

  Trends driving Packaging today, tomorrow

So to deal with industrials’ and consumers’ expectations, two ways are explored. The first solution is the petroleum polymers replacement by biobased polymers. A survey made by IPSOS (2011) analyzed consumers' expectations regarding packaging. To deal with societal expectations, the second solution investigated is the development of functional packaging. As described above, from consumer point of view, packaging materials should protect the food. Limiting food waste is one of the main challenges presented in the European Horizon 2020 program. According to a survey (Canadean 2012) which analyzes the industry’s point of view, the leading drivers of the development of functional packaging in 2012-2013 are "consumer convenience", "safety and traceability" and "enhanced product performance". The COST action FP1405-ActInPak focuses its work to precise these concepts and to understand their industrialization. It aims to identify and focus on the key technical, social, economic and legislative factors relevant for a successful deployment of renewable fiber-based functional packaging solutions.

III-1-2 - Nanocellulose

First, nanocellulose was mainly used to enhance mechanical properties. With changing trends and increased interest in this biomaterial, more applications were explored in the last few years. J.A. Shatkin [et al.] distinguishes three parties in the nanocellulose market: high volume, low volume and emerging applications. Applications with largest potential volume of cellulose nanomaterials are paper and paper packaging, textile, cement and automobile parts. Smaller volume applications include sensors, construction, aerospace materials, cosmetics, pharmaceuticals and paint additives. Novel applications are innovations without current markets and may employ the electrical and photonic properties of cellulose nanomaterials. Additive manufacturing (3D printing) may become a very large volume user of cellulose nanomaterials for toys, architectural models and parts, but more research is required before it can be ready for commercialization.

The requirements of the global ecological transition should stimulate industrial demand for nanocellulose for various applications.

  Identified applications of nanocellulose and their categorization  
  Nanocellulose applications
[Cellulosic biocomposites]

According to a Zion Research's report, global demand for nanocellulose market is expected to reach USD 530.0 million in 2021, growing at a CAGR of around 30.0% between 2016 and 2021.

  Nanocellulose market
[Market Research Store]

III-1-3 - Oxygen scavengers

The food industry uses controlled atmosphere, vacuum packaging and oxygen scavengers to increase the shelf life of food. Regarding oxygen scavengers, the table below analyzes the application possibilities of active agents in food packaging.

System Implementations Characteristics Applications/Examples
Active ingredients into the polymer matrix of the packaging Extrusion, injection of the mixture High temperature, shear stress Plastic beer bottle
Active agents on packaging surface Coating packaging material with active agents High temperature, no shear stress Hamburger packaging
Bagged oxygen absorber in the package Introduction into the package of a gas permeable sachet containing active agents Ease of use Delicatessen, ready meal, cookies

Active agents in food packaging

The oxygen scavenger sachet, cheaper and easier, is the most used in the food industry. Different kinds of products are available depending on the absorption time, the level of absorption (oxygen only or other gas), the humidity or the type of food.

  Commercially available oxygen absorbers  

III-2 - Predictions for using nanocellulose to improve oxygen scavengers

III-2-1 - Competitive analysis

Porter Diagram highlights the competitive strengths of the scavenger coupled with nanocellulose.

  Click on picture to enlarge  

At the center of Porter's diagram, the main technology: control oxygen in the package. Inputs are the raw materials of traditional oxygen absorbers. Bottom, competitive applications of oxygen absorbers. At the top, the new entrant: the nanocellulose-active agent combination. In output, is the final application of the oxygen scavenger in general as well as the customers.

III-2-2 - Strategic diagnosis

Strengths Weaknesses
  • Biobased product
  • Improvement of traditional product
  • No contact with food
  • Panel of applications
  • Nanocellulose very expensive
  • High energy consumption
  • Hydrophilicity
Opportunities Threats
  • Regulation against traditional oxygen scavenger sachet
  • Less food waste
  • Eco-friendly branding
  • Market dominated by oxygen scavenger sachet
  • Competition of plastic barrier packaging

SWOT for nanocellulose-active agent combination

In our study, it seems appropriate to focus on the biobased and ecological aspect of the product, the added value due to the elimination of the oxygen scavenger bag and not on the cost or difficulties of product development. Nevertheless, with the development of new nanocellulose production systems, parameters may change in the near future, hence the strategy too.

III-2-3 - Value chain

  Value chain for the use of oxygen scavenger sachet in food packaging  
  Value chain for the use of the nanocellulose-oxygen absorber combination in food packaging  

The first step is the purchase of raw materials for the manufacture of packaging and oxygen scavengers. It is important to reduce the price of the packaging, as this has a direct impact on the price of the final product paid by the consumer. The better the production line, the lower the price for customers.

IV - Future prospects


Let's identify key variables and development factors affecting projects based on the use of nanocellulose to improve oxygen scavengers in active packaging. Then, let's identify the main actors responsible for and/or affected by these developments. Finally, let's consider the perspectives through three scenarios.

Key variables

Development factors

Main actors

IV-1 - Scenario 1 - 2020: oxygen scavengers coupled with nanocellulose invade the market


April 2019, a massive food poisoning happens in France: oxygen scavengers in bag contaminate the meat. One year later, the European Union banned the use of oxygen scavengers in sachets in food packaging. The use of nanocellulose to improve the oxygen scavenger in active packaging goes on an industrial scale. The Marcus Wallenberg Prize awarded a group of Japanese and French researchers for the design of a less energy-intensive nanocellulose production method. They sell their patent to a pulp mill to produce nanocellulose themselves. In fact, with the decline in paper consumption, the pulp industry has to find new markets. Demand for nanocellulose, now used in many sectors (automobile, building...), is increasing.

This results in a significant decrease in the production cost of nanocellulose. As a result, the oxygen scavenger coupled with nanocellulose has become economically viable.

Probability of occurrence: 72 %

IV-2 - Scenario 2 - 2020: nanocellulose penetrates slowly the oxygen scavengers’ market


As predicted in 2015 by one of Wall Street's masters of energy, Andrew John Hall, the end of the shale oil boom signals the return of conventional oil. The sanctions against Iran are no longer relevant. The price of a barrel falls below $ 20, which is $ 30 below the break-even point for shale oil. Most Western companies are affected by bankruptcy, leaving control of the oil market to Saudi Arabia and Iran. The price per barrel reaches 60 dollars in 2020. At the same time, consumer interest in sustainable development is increasing. Biopolymers are gradually replacing petrochemical materials.

On the initiative of a consumer association, a label is affixed to packaging made of bio-based materials with ecological oxygen scavengers. An approach poorly known by the population because of the lobbying of agri-food manufacturers who enter into agreements with producers of oxygen scavengers. In addition, oxygen scavengers coupled with nanocellulose remain more expensive. As a result, the majority of packaging manufacturers continue to use oxygen scavengers in bag.

Probability of occurrence: 62 %

IV-2 - Scenario 3 - 2020: active agents coupled to nanocellulose have no future


The work of the research laboratory LGP2 specializes in biobased materials including nanocellulose do not bring innovations economically interesting on the market of oxygen scavengers. Nanocellulose-oxygen scavenger coupling remains difficult on an industrial scale. In addition, the price of oil has never been so low: $ 25 per barrel. Packaging made of biobased materials is not economically viable because plastic remains less expensive than bioplastics. Research in biosourced is less and less funded and the demand for nanocellulose too low in the packaging, medical or automotive sectors to maintain a good level of production. Nanocellulose manufacturers abandon their optimization efforts. Agri-food groups prefer to use the oxygen scavenger in bag they are used to and do not want to invest in new machines to introduce nanocellulose into packaging.

Probability of occurrence: 63 %

V - Conclusion


Nanocellulose has a promising future in active packaging. Although the use of fossil fuels is still the dominant model, the development of products from renewable plant resources is evident in the global ecological logic.

All industrial sectors are concerned by the new slogan "green your business". It is natural that the packaging industry is moving towards more sustainable and functionalized packaging.

The combination nanocellulose-oxygen sensor offers a safer technical solution because the nanocellulose enhances the retention and absorption of oxygenating agents. This duo allows different solutions of form, coating, insertion in the matrix or grafting, for applications in various markets. It can now replace oxygen scavengers in sachets, reassuring consumers worried about possible contacts of the bag with food.

VI - Bibliography-Webography


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    Global nanocellulose (nano-crystalline cellulose, nano-fibrillated cellulose and bacterial nanocellulose) market set for rapid growth, to reach around USD 530.0 million by 2021.   Market Research Store, 15 April 2016
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