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Cationic emulsions of maleic anhydride derivatives of oleic and abietic acid for hydrophobic sizing of paper, TAPPI Journal 2020
ABSTRACT: Ordinary rosin sizing agents are mixtures of resin acids that include abietic acid and related compounds obtained from softwoods such as pine. Fatty acids, which are another byproduct of the kraft pulping of soft-wood species, also may have hydrophobic effects, but their use as sizing agents has seldom been considered. In the current study, abietic acid and oleic acid, in the absence of other components, were first modified by reaction with maleic acid anhydride. Then, the maleated derivatives (maleated oleic acid [MOA] and maleated abietic acid [MAA]), which were emulsified with cationic starch at the 1:1 and 3:2 ratio, respectively, were added to fiber furnish containing aluminum sulfate (papermaker’s alum). The prepared sheets were dried with a rotating drum on one side at 100°C at low pressure to cure the sizing agents. The chemical, optical strength, and absorption properties were measured. The presence of the sizing material was confirmed using time of flight secondary ion mass spectrometry (ToF-SIMS), and the retention of the sizing agent on fibers was supported by evidence of hydrocarbons on the paper surface. In addition to achieving sufficient water resistance features with MAA, a lesser hydrophobic character was obtained when using MOA. Compared to commercial applications, relatively large amounts of sizing agent were used to obtain a sufficient sizing degree. The MOA required 5% addition to achieve a similar sizing degree as MAA at the 2% level. The sizing treatments also resulted in substantial increases in tensile index value. Since cationic starch was used in the formulation of the sizing agents, the increase in tensile index may have been due to the influence of cationic starch. Contributions to paper strength from a combination of ionic complexation and mutual association of hydrophobic groups is also proposed. Depending on the amount of sizing agent, the yellowness increased, especially when sizing with MOA.
Journal articles
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Multifunctional barrier coating systems created by multilayer curtain coating, TAPPI Journal November 2023
ABSTRACT: Functional coatings are applied to paper and paperboard substrates to provide resistance, or a barrier, against media such as oil and grease, water, water vapor, and oxygen, for applications such as food packaging, food service, and other non-food packaging. Today, there is increasing interest in developing recyclable and more sustainable approaches for producing these types of packages. This paper focuses on water-based barrier coatings (WBBC) for oil and grease resistance (OGR), water, moisture vapor transmission rate (MVTR), and oxygen barrier performance. The main goal is to create coated systems that can achieve more than one barrier property using multilayer curtain coating (MLCC) in a single application step. One advantage is in optimizing coating material cost with the use of functional chemistry in confined layers where performance is balanced within the coating layered structure. This allows simultaneous application of layers of different polymer types in one step to achieve the appropriate performance needs for a given barrier application. This paper provides working examples of using MLCC to create coating structures with multiple barrier properties in a single application pass. Barrier polymers studied include styrene butadiene, styrene acrylate, starch-containing emulsions, and polyvinyl alcohol. The paper also shows the effect of increasing the pigment volume concentration with platy clay or fine ground calcium carbonate on MVTR and OGR barrier properties.
Journal articles
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Surface energy considerations for offset printing of coated paper and paperboard, TAPPI Journal November 2023
ABSTRACT: Offset printing of coated paper involves the complex interactions of ink with a surface that is characterized by three major properties: roughness, porosity, and related pore network structure and surface chemistry (related to surface free energy [SFE]). The effects of porosity and roughness are relatively well understood and are documented in the literature, whereas the influence of surface chemistry is much less studied and therefore the focus of this paper. The key results shown include: i) Coating porosity has a negligible effect on SFE determination by contact angle using two fluids. ii) The chemistry of the latex polymer in the coating formulation dominates the influence on SFE compared to pigment, with any surface energy differences present in the pigment being almost completely masked by latex. iii) Wetting agent and corona treatment can impact water absorption rate and surface spreading of water, resulting in small differences in printability. Increasing the concentration of the surfactant on a coated surface indicates switching orientation of the surfactant molecules, giving a “step wise” printing result. When looking to improve offset printability by selection of different pigments, the variation in SFE is less important than variation in either surface roughness or porosity.
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Cross-flow separation characteristics and piloting of graphene oxide nanofiltration membrane sheets and tubes for kraft black liquor concentration, TAPPI Journal September 2023
ABSTRACT: Dewatering of weak black liquor (WBL) in the kraft cycle by evaporation is highly energy intensive. Membranes are an attractive alternative for energy-efficient dewatering, but existing commercial polymeric or ceramic membranes are either degraded in BL or have high capital costs. Our recent works have demonstrated the engineering of graphene oxide (GO) nanofiltration membranes, their stability and promising performance in BL conditions, and preliminary scale-up into sheets and tubes. Here, we describe in detail the separation characteristics of GO membrane sheets and tubes under real BL conditions and crossflow operation. Recycle-mode piloting of a GO tubular membrane showed average “production flux” of 16 L/m2/h (LMH) and high rejections of lignin (98.3%), total solids (66%), and total organic carbon (83%), with no signs of irreversible fouling identified. A corresponding GO sheet membrane produced an average flux of ~25 LMH and maintained high lignin rejection of ~97% during a slipstream pilot at a kraft mill site using WBL with ~16 wt% total solids (TS). Finally, we piloted a Dow/DuPont XUS1808 polyamide composite reverse osmosis (RO) membrane for last-mile processing of the GO nanofiltration membrane permeate. The RO membrane showed a steady state flux of 19 LMH at 65 bar and produced ~0.02 wt% TS water product, which is highly suitable for reuse in pulp washing operations in the kraft process. The results have strong positive implications for the industrial application of GO membranes in BL concentration and other related applications.
Journal articles
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Control of continuous digester kappa number using generalized model predictive control, TAPPI Journal September 2024
ABSTRACT: Kappa number variability at the digester impacts pulp yield, physical strength properties, and lignin content for downstream delignification processing. Regulation of the digester kappa number is therefore of great importance to the pulp and paper industry. In this work, an industrial application of model-based predictive control (MPC), based on generalized prediction control, was developed for kappa number feedback control and applied to a dual vessel continuous digester located in Western Canada. The problem was complicated by the need to apply heat at multiple locations in the cook. In this study, the problem was reduced from a multiple to a single input system by identifying three potential single variable permutations for temperature adjustment. In the end, a coordinated approach to the heaters was adopted. The process was perturbed and modeled as a simple first order plus dead time model and implemented in generalized predictive control (GPC). The GPC was then configured to be equivalent to Dahlin’s controller, which reduced tuning parameterization to a single closed loop time constant. The controller was then tuned based on robustness towards a worst-case dead time mismatch of 50%. The control held the mean value of the kappa number close to the setpoint, and a 40% reduction in the kappa number’s standard deviation was achieved. Different kappa number trials were run, and the average fiberline yield for each period was evaluated. Trial results suggested yield gains of 0.3%•0.5% were possible for each 1 kappa number target increase.
Journal articles
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Study on the effect of aluminum diethyl phosphinate in synergy with ammonium polyphosphate on the flame retardancy of cellulose paper, TAPPI Journal April 2025
ABSTRACT: This paper involved the synergistic incorporation of ammonium polyphosphate (APP) and diethyl aluminum phosphinate (AlPi) as flame-retardant fillers for producing flame-retardant paper. The research revealed that APPs were square particles with a smooth surface, and their solubility was 0.29 g/100 mL at 20°C, which increased to 4.12 g/100 mL at 60°C. The surfaces of AlPis were rough and irregular. The solubility of AlPi was 0.023 g/100 mL at 20°C, and the solubility remained stable when the temperature increased. The addition of AlPi had a minor influence on the pulp beating degree. The tensile strength of kraft/APP/AlPi decreased with the increase of the AlPi addition. For a paper with 20 wt% APP and 0 wt% AlPi, the limiting oxygen index (LOI) value was 27.2%, and it burned completely at the eighth second during vertical combustion. When the AlPi additive content increased to 20 wt%, its LOI value increased to 32.2%, and the vertical combustion self-extinguished as soon as the flame was removed. Scanning electron microscopy (SEM) showed that the char residue of the kraft/APP/AlPi had a more complete fiber network structure than that of kraft/APP. The Raman spectroscopy indicated that the area ratio of the D (amorphous phase; disordered graphite vibration) band to the G (crystal phase; graphite carbon vibration) band (ID/ IG) ratio of kraft/APP/AlPi was lower than that of kraft/APP, meaning that the graphitization degree of the char residue of kraft/APP/AlPi was higher than that of kraft/APP, which indicated the kraft/APP/AlPi had better flame retardancy.
Journal articles
In-situ process monitoring in deep-drawing of paper using partially transparent tools, TAPPI Journal August 2025
ABSTRACT: The production of three-dimensionally formed packaging from paper by deep drawing usually leads to the occurrence of wrinkles, which result from the high tangential compressive stresses in the flange area and the limited flowability of the material. Wrinkles, although mostly tolerated in industry, end in both a reduced visual appearance and a reduction in usability for packaging, as with, for example, when gas-tightness is required. Previous research efforts have been limited to determining the wrinkle distribution after completion of forming and removal of the formed part. Consequently, the possibility of understanding the sequence of formation of individual wrinkles in the inhomogeneous material is lost. To remedy this situation, a method for local in-situ process monitoring is presented. Using a transparent die and an industrial camera, the flange area can be observed during the forming process. An image processing algorithm is applied to analyze the local development of the deep drawing process from the continuously recorded image data. The method described can be used to analyze the draw-in behavior and wrinkle formation locally and continuously over the drawing depth. The blank holder force influences the draw-in and the wrinkle pattern both locally and throughout the drawing process. A more precise understanding of the wrinkle formation will allow for more efficient process control in the future.
Journal articles
Colloidal silica and its effects during formation of paper sheets in the presence of nanofibrillated cellulose, cationic starch, and cationic acrylamide copolymer, TAPPI Journal May 2025
ABSTRACT: This work considered effects of colloidal silica addition during laboratory preparation of paper sheets containing nanofibrillated cellulose (NFC) that had been pretreated with cationic starch. The emphasis was on process performance issues, including dewatering rates, fine particle retention, and the extent of fiber flocculation. In addition, micrographs were obtained to show what was happening to the NFC upon treatments with cationic starch and subsequent application of hydrodynamic shear. Contrasting results were obtained, depending on the charge density of the cationic starch. Pretreatment of the NFC with a high charge density cationic starch (degree of substitution 0.2) resulted in strong interactions with the colloidal silica, enhancing the dewatering rate and contributing to fine-particle retention. The medium charge cationic starch pretreatment led to effects suggesting a bridging mechanism of action, and subsequent colloidal silica had no significant effect on dewatering. Treatment of that system with a high level of colloidal silica (0.2%) resulted in lower retention. In general, the final colloidal silica treatments tended to decrease the level of flocculation in the suspensions, giving more uniform handsheets. Mechanisms, some of them related to the clustering and dispersion of cationic starch-treated NFC, were proposed to account for the observed effects.
Journal articles
Magazine articles
Gas dispersion in the oxygen delignification process, TAPPI Journal May 2021
ABSTRACT: There has been very little knowledge about the state of gas dispersion in the oxygen delignification process, even though this has a major impact on the performance of the reactor. This paper presents a new continu-ous inline method for measuring oxygen bubble size distribution in the reactor, as well as results from studies con-ducted in softwood and hardwood lines. This new measurement worked well, and new information about oxygen bubble size, as well as how different reactor conditions affected the distribution, was obtained. For example:œ In the softwood line, the mean volume-weighted bubble size was about 0.1 mm, whereas in the hardwood line, this size was almost 10 times higher. For both lines, there was considerable variation in the measured bubble size over the long term.œ For both lines, an increase in mixer rotation speed caused a discernible decrease in the bubble size, and an increase in oxygen charge caused a discernible increase in the bubble size.œ In the softwood line, no coalescence of the bubbles in the reactor was observed, but in the hardwood line, some coalescence of the larger bubbles occurred.œ In the test conducted in the hardwood line, the use of brownstock washer defoamer caused a discernible increase in oxygen bubble size.œ In the hardwood line, reactor pressure had a noticeable effect on the amount of delignification, which indicated that improving mass transfer of oxygen (e.g., by decreasing the oxygen bubble size, in this case) should also have an increasing effect on the delignification.
Journal articles
Magazine articles
The role of gas dispersion in the oxygen delignification process, TAPPI Journal May 2021
ABSTRACT: Oxygen delignification is an essential part of the pulp production process. Delignification occurs with the aid of alkali and dissolved oxygen. Dissolved oxygen is obtained by dispersing oxygen gas into the pulp suspension by using efficient mixers. Little is known about the state of oxygen gas dispersion and its effect on oxygen delignification kinetics and efficiency. This paper will present the results for the effect of gas bubble size on the performance of oxygen delignification. The results are mainly based on detailed studies made in a Finnish hardwood mill where the oxygen bubble size distribution could be altered at the feed of the reactor. An essential aspect of these studies was the use of a new continuous inline gas bubble size measurement system to simultaneously determine the bubble size distribution at the feed and top of the reactor. Information about oxygen consumption in the reactor could also be obtained through the bubble size measurements. Accordingly, these studies quantify the effect of oxygen bubble size on the kappa reduction of the pulp. The effect of different chemical factors on the oxygen bubble size is also studied.Finally, the relationship between the gas bubble size and the liquid phase oxygen mass transfer coefficient (kLa) is presented. This connects the bubble size to the kappa reduction rate. Based on the presented modeling approach and the evaluation of practical factors that are not taken into account in the modeling, it was concluded that the volumetric average oxygen bubble size should preferably be smaller than 0.2 mm in practice.The information obtained with the new gas bubble size measurement system and the presented modeling approach give a very new basis for understanding, monitoring, adjusting, and designing oxygen delignification processes.